KR100716652B1 - Capacitor with nano-composite dielectric and method for manufacturing the same - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention provides a capacitor having a nanocomposite dielectric film capable of obtaining high dielectric constant while having excellent leakage current characteristics and being applicable to all capacitors including a concave structure, and a method of manufacturing the dielectric film of the capacitor of the present invention. Is a dielectric film having a dielectric constant of HfO ₂ and at least the dielectric constant of HfO ₂ (ZrO ₂ , La ₂ O _3, or Ta ₂ O ₅ is 25-30, and the bandgap energy is 4.3-7.8). By including the nano-composite dielectric film mixed in the form, it is possible to produce a capacitor having a high dielectric constant while ensuring leakage current characteristics without loss of dielectric constant even in a relatively thin thickness.

Capacitor, Dielectric Film, Nanocomposite, HfO₂, HfZrO

Description

Capacitor with nanocomposite dielectric film and manufacturing method therefor {CAPACITOR WITH NANO-COMPOSITE DIELECTRIC AND METHOD FOR MANUFACTURING THE SAME}

1 is a view showing a capacitor having a HfO ₂ / Al ₂ O ₃ dielectric film according to the prior art,

2 is a view showing the dielectric constant of the HfAlO nanocomposite dielectric film according to the prior art,

3 is a view showing a concept of a nanocomposite dielectric film of the present invention,

4 is a view for explaining the atomic layer deposition method of the HfZrO nanocomposite dielectric film according to the first embodiment of the present invention,

FIG. 5 illustrates the structure of the HfZrO nanocomposite dielectric film deposited by FIG. 4;

6 is a diagram showing the dielectric constant of the HfZrO nanocomposite dielectric film of the present invention,

7 is a view for explaining the atomic layer deposition method of the HfLaO nanocomposite dielectric film according to a second embodiment of the present invention,

FIG. 8 shows the structure of the HfLaO nanocomposite dielectric film deposited by FIG.

9 is a view for explaining the atomic layer deposition method of the HfTaO nanocomposite dielectric film according to a third embodiment of the present invention,

10 is a view showing the structure of the HfTaO nanocomposite dielectric film deposited by FIG.

FIG. 11 shows the structure of a capacitor employing the HfZrO nanocomposite dielectric film of the present invention. FIG.

* Explanation of symbols for the main parts of the drawings

21: lower electrode

22: HfZrO nanocomposite dielectric film

23: upper electrode

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to semiconductor manufacturing technology, and more particularly, to a capacitor having a nano-composite dielectric film in which two dielectric films are mixed in the form of a nanocomposite, and a method of manufacturing the same.

Recently, as the integration of memory products has accelerated due to the development of miniaturized semiconductor process technology, the unit cell area has been greatly reduced, and the operating voltage has been reduced. However, the charging capacity required for the operation of the memory device, despite the reduction in cell area, sufficient capacity of 25pF / cell or more is continuously required to prevent the occurrence of soft errors and shortening of the refresh time. have. Therefore, in the case of the NO capacitor element for DRAM that uses a silicon nitride film (Si ₃ N ₄ ) deposited using Di-Chloro-Silane (DCS) gas as a dielectric, it has a three-dimensional electrode surface having a hemispherical structure with a large surface area. Despite the use of form storage nodes, their height continues to increase.

On the other hand, since the NO capacitor shows a limit in securing the charge capacity required for the next-generation DRAM capacitor of 256M or more, a capacitor element or a storage node employing a dielectric film having a high dielectric constant such as Ta ₂ O ₅ , Al ₂ O ₃ , HfO _2, etc. The research to develop the structure of the three-dimensional structure (cylinder, concave) is in full swing.

However, Ta ₂ O ₅ has a weak leakage current characteristic, and Al ₂ O ₃ (ε = 9) has a good leakage current characteristic, but the dielectric constant is not very large, thereby limiting the charging capacity and having a relatively large dielectric constant. HfO ₂ (ε = 25) is excellent in securing the charging capacity but has a problem in that the durability of the capacitor is inferior because the breakdown field strength is vulnerable to repetitive electric shock.

In order to solve this problem, a capacitor having a stacked structure such as HfO ₂ / Al ₂ O ₃ , that is, a double dielectric layer structure, has been proposed.

1 is a view showing a capacitor having a HfO ₂ / Al ₂ O ₃ dielectric film according to the prior art.

As shown in FIG. 1, the dielectric film 12 of the capacitor positioned between the lower electrode 11 and the upper electrode 13 has a double dielectric film structure in which Al ₂ O ₃ (12a) and HfO ₂ (12b) are stacked. Have

Al ₂ O ₃ is manufactured in nano-composite form in devices below 80nm class with low dielectric constant and added to reduce leakage current.It is excellent to 80nm class devices because leakage current is secured even in physical thin thickness. Applicable due to mass productivity and electrical characteristics. However, scaling of the equivalent oxide thickness (Tox.eq) is further required in a capacitor of a DRAM using a concave structure, which is not applicable to the concave structure.

In order to apply to a capacitor having a concave structure, a dielectric film in which HfO ₂ and Al ₂ O ₃ are mixed at a constant composition ratio, that is, HfO ₂ _Al ₂ O ₃ nanocomposite concept is recently deposited (hereinafter referred to as' HfAlO nanocomposite dielectric film). Is used as a dielectric film of a capacitor.

However, in this case, there is a problem that the dielectric constant of the HfAlO nanocomposite dielectric film has a low value of about 13 to 15.

2 is a view showing the dielectric constant of the HfAlO nanocomposite dielectric film according to the prior art.

As shown in FIG. 2, the dielectric constant of HfO ₂ is 25 and the dielectric constant of Al ₂ O ₃ is 9, but HfAlO (Hf: Al = 1: HfO ₂ and Al ₂ O ₃ mixed in the form of a nanocomposite) is shown. 1) The nanocomposite dielectric film has a dielectric constant of 13 to 15.

According to the results shown in FIG. 2, the HfAlO nanocomposite dielectric film has a value very lower than the dielectric constant of HfO ₂ , that is, a loss of dielectric constant of HfO ₂ mixed in the HfAlO nanocomposite dielectric film occurs and the nanocomposite is used in a device of 80 nm or less. It is not possible to secure the high permittivity of the dielectric film.

As such, the reason why the HfAlO nanocomposite dielectric film exhibits a lower value than the dielectric constant value of HfO ₂ is because Al ₂ O ₃ having a very low dielectric constant is mixed.

Therefore, there is a need for a dielectric film that is excellent in leakage current characteristics and has a high dielectric constant equal to that of HfO ₂ , but is applicable to all capacitors including a concave structure.

The present invention has been proposed to solve the above problems of the prior art, a capacitor having a nanocomposite dielectric film having excellent leakage current characteristics and applicable to all capacitors including a concave structure and attaining a high dielectric constant. It is an object to provide a manufacturing method.

The dielectric film of the capacitor of the present invention for achieving the above object is characterized in that the dielectric film having a dielectric constant equal to the dielectric constant of HfO ₂ and at least the HfO ₂ comprises a nanocomposite dielectric film mixed in the form of a nanocomposite, the dielectric film has a dielectric constant And 25 to 30, and a band gap energy of 4.3 to 7.8, wherein the dielectric film is selected from ZrO ₂ , La ₂ O _3, or Ta ₂ O ₅ , and the nanocomposite dielectric film is HfO _2. And the dielectric film are each mixed by having a thickness of 1 Å to 5 당 per deposition cycle by atomic layer deposition.

The dielectric film manufacturing method of the capacitor is a nanocomposite dielectric film in which HfO ₂ and the dielectric film are mixed in nanocomposite form by repeating the [HfO ₂ deposition cycle] and [dielectric film deposition cycle] y and z times, respectively, using atomic layer deposition. And depositing annealing step for densification of the nanocomposite dielectric film, wherein the dielectric film deposited by the [dielectric film deposition cycle] is selected from ZrO ₂ , La ₂ O _3, or Ta ₂ O ₅ . The ratio of y and z is 1:10 to 10: 1, and the HfO ₂ and the dielectric film are respectively deposited per deposition cycle so that the thickness of the nanocomposite dielectric film is 25 kW to 200 kW. It is characterized in that it is deposited several times with a thickness of 1Å ~ 5Å and mixed in the form of nanocomposite.

Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the technical idea of the present invention. .

The present invention described below has excellent leakage current characteristics of Al ₂ O ₃ level, secures a high dielectric constant (ε = 20 or more) at the same level as the dielectric constant of HfO ₂ , and is applicable to all capacitors including a concave structure. A dielectric film applicable to ultra-high density semiconductor devices of 70 nm or less is proposed.

3 is a diagram illustrating the concept of the nanocomposite dielectric film of the present invention. Here, the nano-composite dielectric to be introduced in the present invention refers to a dielectric film in which the first dielectric film and the second dielectric film are mixed in a nanocomposite form, rather than being formed in a stacked form.

3, the nano-composite dielectric of the present invention has a first element (M ₁₎ a first dielectric layer containing a (M ₁ O) and the second dielectric layer containing a second element (M ₂₎ (M ₂ O) is mixed in the form of nanocomposite, and thus the first dielectric film (M ₁ O) and the second dielectric film (M ₂ O) are mixed in the form of nanocomposite so that the first dielectric film (M ₁ O) and the second dielectric film (M _The M ₁ M ₂ O nanocomposite dielectric film, which is a new oxide material including the first element (M ₁ ) and the second element (M ₂ ), does not have the property of ₂ O). Here, in the M ₁ M ₂ O nanocomposite dielectric film, 'M ₁ ' means the first element, 'M ₂ ' means the second element, and 'O' means oxygen.

The M ₁ M ₂ O nanocomposite dielectric film described in FIG. 3 selects the first element M ₁ and the second element M ₂ to have a dielectric constant (at least 20) greater than that of the HfAlO nanocomposite dielectric film. .

For example, the first element M ₁ is selected as Hf, and the second element M ₂ is selected from Zr, La, or Ta.

Accordingly, the M ₁ M ₂ O nanocomposite dielectric film of the present invention can be HfZrO, HfLaO or HfTaO, and these M ₁ M ₂ O nanocomposite dielectric films have a dielectric constant (at least 15 to 15) of the HfAlO nanocomposite dielectric film. 20 or more).

Table 1 below compares permittivity, band gap energy, and CBO according to the types of dielectric films.

Dielectric film permittivity Band gap energy (Eg, ev) CBO to Si (eV) SiO ₂ 3.9 8.9 3.5 Si ₃ N ₄ 7 5.1 2.4 Al ₂ O ₃ 9 8.7 2.8 Y ₂ O ₃ 15 5.6 2.3 ZrO ₂ 25 7.8 1.4 HfO ₂ 25 5.7 1.5 Ta ₂ O ₅ 26 4.5 0.3 La ₂ O ₃ 30 4.3 2.3 TiO ₂ 80 3.5 0.0

 In Table 1, 'CBO to Si' is a measure of how difficult it is to extract electrons. The lower the value, the better the leakage current characteristic, and the larger the band gap energy, the better the leakage current characteristic. When the dielectric film is amorphous at room temperature, the dielectric film is advantageous in terms of the conduction path, so that the leakage current is small. However, a large dielectric constant requires crystallinity, and thus the dielectric constant and amorphous have a trade-off relationship.

As can be seen from Table 1, since SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , and Y ₂ O ₃ have a dielectric constant of 20 or less, the high charge capacity required for the capacitor dielectric film of a highly integrated semiconductor device cannot be realized. , ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , La ₂ O ₃ , and TiO ₂ have a dielectric constant of 20 or more, thereby realizing a high charge capacity required in a capacitor dielectric film of a highly integrated semiconductor device.

However, when ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , La ₂ O ₃ and TiO ₂ are used alone or in a laminate, problems such as loss of dielectric constant, degradation of leakage current characteristics, and limitations of the structure of the applied capacitors Have

Therefore, in the present invention, the dielectric constant is 20 or more, thereby realizing the high charge capacity required for the capacitor dielectric film of the highly integrated semiconductor device, and having excellent leakage current characteristics without loss of dielectric constant of the mixed dielectric films (especially HfO ₂ ), and of all capacitors. An amorphous nanocomposite dielectric film applicable to the structure is formed.

According to Table 1, the nanocomposite dielectric film of the present invention can be HfZrO, HfLaO or HfTaO, and these nanocomposite dielectric films have a dielectric constant (at least 20 or more) larger than the dielectric constants 13 to 15 of the HfAlO nanocomposite dielectric film. Here, HfZrO, HfLaO or HfTaO commonly includes Hf, where HfZrO, HfLaO or HfTaO is HfO ₂ (dielectric constant 25), ZrO ₂ (dielectric constant 25), La ₂ O ₃ (dielectric constant 30) or Ta ₂ O ₅ ( This is because the dielectric constant 26) is mixed in the form of nanocomposite. Thus, HfZrO, HfLaO or HfTaO has a dielectric constant of at least 20 or more without losing the dielectric constant of HfO ₂ . On the other hand, HfAlO nanocomposite dielectric layer is brought to a lower dielectric constant than HfO ₂ resulted in the loss of the dielectric constant HfO ₂ having a mixture of Al ₂ O ₃ of a dielectric constant of 9 to HfO ₂ is a dielectric constant of 25.

Meanwhile, in Table 1, TiO _{2, which} has the highest dielectric constant of 80, may also be mixed with HfO ₂ to form a nanocomposite dielectric film. However, TiO ₂ has a lower band gap energy (Eg) than other dielectric films, which is 70 nm or less. It is impossible to obtain a Tox.eq of 10 dB or less, which is necessary for a device having a design rule, thereby lowering the electrical characteristics of the capacitor.

As described above, the M ₁ M ₂ O nanocomposite dielectric film of the present invention includes a first dielectric film (M ₁ O) including a first element (M ₁ ) in order to have a mixed structure in a nanocomposite form, not a stacked form. And a second dielectric layer (M ₂ O) including the second element (M ₂ ) is formed using an atomic layer deposition (ALD).

In the following embodiments, the atomic layer deposition method and structure of the HfZrO, HfLaO, and HfTaO nanocomposite dielectric film are described.

4 is a view for explaining the atomic layer deposition method of the HfZrO nanocomposite dielectric film according to the first embodiment of the present invention, the concept of supplying a gas into the chamber when the HfZrO nanocomposite dielectric film is formed by atomic layer deposition to be.

As is well known, Atomic Layer Deposition (ALD) first supplies a source gas, which chemically adsorbs a layer of source onto the substrate surface, and the extra physically adsorbed sources shed purge gas. After purging, supply a reaction gas to one layer of the source to chemically react one source and the reaction gas to deposit the desired atomic layer, and the excess reaction gas flows through the purge gas to purge the thin film in one cycle. Deposit. As described above, in the atomic layer deposition method, not only a stable thin film but also a uniform thin film can be obtained by using a surface reaction mechanism. In addition, since the source gas and the reaction gas are separated from each other and sequentially injected and purged, it is known to suppress particle generation due to gas phase reaction compared to chemical vapor deposition (CVD).

The unit cycle of the atomic layer deposition process for depositing the HfZrO nanocomposite dielectric film is as follows.

[Unit cycle 1]

[(Hf source / purge / oxidant exposure / purge) _y (Zr source / purge / oxidant exposure / purge) _z ] _n

In unit cycle 1, the Hf source is a pulse for supplying an Hf source for forming HfO ₂ , the Zr source is a pulse for supplying a Zr source for forming ZrO ₂ , and y determines a film thickness of HfO ₂ ( Number of cycles of Hf source / purge / oxidant exposure / purge), z denotes the number of cycles (Zr source / purge / oxidant exposure / purge) that determine the film thickness of ZrO ₂ , and n denotes the thickness of the HfZrO dielectric film. Indicates the number of cycles.

Looking closely at unit cycle 1, the (Hf source / purge / oxidant exposure / purge) _y cycle refers to the HfO ₂ deposition cycle that repeats the cycle consisting of Hf source, purge, oxidant exposure and purge y times, and (Zr source / Purge / Oxidant Exposure / Purge) The _z cycle refers to a ZrO ₂ deposition cycle in which _z cycles of Zr source, purge, oxidant exposure and purge are repeated z times. By repeating each deposition cycle as described above y and z times, HfO ₂ and ZrO ₂ of the required thickness are deposited respectively, and HfZrO nano is performed by performing n times of integrated deposition cycles of HfO ₂ deposition cycle and ZrO ₂ deposition cycle. Determine the total thickness of the composite dielectric film.

The deposition example of the HfZrO nanocomposite dielectric film will be described in detail with reference to FIG. 4.

Before describing the deposition process, the HfO ₂ deposition cycle is (Hf / N ₂ / O ₃ / N ₂ ) as a unit cycle and the unit cycle is repeated y times. In the unit cycle, Hf is an Hf source, N ₂ is a purge gas, and O ₃ is an oxidant gas.

In the ZrO ₂ deposition cycle, (Zr / N ₂ / O ₃ / N ₂ ) is a unit cycle, and the unit cycle is repeated z times. In the unit cycle, Zr is a Zr source, N ₂ is a purge gas, and O ₃ is an oxidant gas.

The HfO ₂ deposition cycle and the ZrO ₂ deposition cycle proceed in a chamber that maintains a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C.

First, the deposition of HfO ₂ will be described. After vaporizing an Hf source selected from HfCl ₄ , Hf (NO ₃ ) ₄ , Hf (NCH ₂ C ₂ H ₅ ) _4, or Hf (OC ₂ H ₅ ) ₄ in a vaporizer, The Hf source is adsorbed by flowing 0.1 seconds to 3 seconds into a chamber that maintains a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove the unreacted Hf source, and the adsorbed Hf source and O are flowed by oxidizing O ₃ gas for 0.1 seconds to 3 seconds. Induce a reaction between ₃ to deposit HfO ₂ . Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted O ₃ and the reaction byproduct.

Cycloalkyl Hf source, N ₂ purge, O ₃ supplied, N units of the _second purge process as described above, and subjected to a cycle unit of y-repeated to deposit a desired thickness of HfO ₂ (1Å~5Å). As the oxidant, H ₂ O vapor may be used in addition to O ₃ , and an inert gas such as argon (Ar) may be used in addition to nitrogen (N ₂ ) as the purge gas.

Next, ZrO ₂ deposition will be described. The Zr source is TEMAZ [Zr {N (CH ₃ ) (C ₂ H ₅ )} with a substrate temperature of 100 ° C to 450 ° C and a pressure of 0.1torr to 10torr. ₄ ] is flowed into the chamber for 0.1 to 3 seconds to adsorb TEMAZ to the substrate. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted TEMAZ, and an O ₃ gas, which is an oxidant, is flowed for 0.1 seconds to 3 seconds, and the adsorbed TEMAZ and O _{3 are} adsorbed. ZrO ₂ in atomic layer is deposited by inducing a reaction of. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted O ₃ and the reaction byproduct.

To deposit a Zr source, N ₂ purge, O ₃ supplied to the process cycles of N ₂ purge unit, and perform the unit cycle z times repeatedly ZrO ₂ having a desired thickness (1Å~5Å) as described above. Here, in addition to the above-described TEMAZ, TDEAZ [Zr {N (C ₂ H ₅ ) ₂ } ₄ ] may be used as the Zr source of ZrO ₂ . In addition to O ₃ , H ₂ O vapor may be used as the oxidant, and inert gas such as argon (Ar) may be used as the purge gas.

FIG. 5 is a diagram illustrating the structure of the HfZrO nanocomposite dielectric film deposited by FIG. 4.

Referring to FIG. 5, the HfZrO nanocomposite dielectric layer is not formed by stacking HfO ₂ and ZrO ₂ in a layer by layer concept, but has a structure in which HfO ₂ and ZrO ₂ are mixed in a nanocomposite form.

The reason for having the mixed structure in the form of nanocomposite is because HfO ₂ and ZrO ₂ are deposited by using the atomic layer deposition method of FIG. 4, in particular, the number of HfO ₂ deposition cycles (y) and the number of ZrO ₂ deposition cycles (z). This is because HfO ₂ and ZrO ₂ are formed to have a thickness of 1 kPa to 5 kPa, respectively. Here, the thickness of 1Å to 5Å of HfO ₂ and ZrO ₂ is the thickness of each film formed discontinuously. In case of depositing thicker than 5Å, HfO ₂ and ZrO ₂ are stacked to form a layer by layer. It becomes a structure.

In order to form the HfZrO nanocomposite dielectric film in which HfO ₂ and ZrO ₂ are mixed using the atomic layer deposition method, the following conditions must be satisfied.

First, HfO ₂ and ZrO ₂ in the nanocomposite (Nano-composite) to increase the effect (Hf source / purge / oxidant exposure / purge) HfO ₂ formed by the _y-cycle and (Zr source / purge / oxidant exposure / purge The thickness of ZrO ₂ formed by the _z cycle is 1 kPa to 5 kPa. In this case, when the thickness of each film is thicker than 5 GPa, each film exhibits an independent characteristic-continuous film- and thus may exhibit the same or deteriorated characteristics as the conventional HfO ₂ / ZrO ₂ laminated dielectric film.

Second, for the nano-composite structure in which HfO ₂ and ZrO ₂ are mixed, not the concept of layer by layer, the (Hf source / purge / oxidant exposure / purge) _y cycle and (Zr source / purge) / Oxidant exposure / purge) The number of cycles y and z in the _z cycle is 10 or less. In other words, the ratio y: z is set to 1:10 to 10: 1.

As described above, when y and z are less than or equal to 10, HfO ₂ and ZrO ₂ are not laminated but form a mixed nanocomposite, thereby forming a new composite material, HfZrO nano, which is neither ZrO ₂ nor HfO ₂ . A composite dielectric film is formed. In addition, when the ratio of y: z, which is the deposition cycle ratio, is set to 1:10 to 10: 1, HfO ₂ and ZrO ₂ can be deposited at a thickness of 1 kPa to 5 kPa, respectively.

As described above, when the HfZrO nanocomposite dielectric film is deposited to a thickness of 1 Å to 5 각각 by controlling the deposition cycle ratio (y: z = 1: 10 to 10: 1) through atomic layer deposition, the mixture is deposited into a nanocomposite form. Compared to the HfO ₂ , ZrO ₂ or HfO ₂ / ZrO ₂ laminates, the crystallization temperature is higher, and it can withstand high temperatures, and the dielectric properties are excellent. Here, the improvement of the dielectric properties can be seen from FIG. 6 after the dielectric constant of the HfZrO nanocomposite dielectric film is measured at 25 levels.

6 is a diagram showing the dielectric constant of the HfZrO nanocomposite dielectric film of the present invention.

As shown in FIG. 6, the dielectric constant of HfO ₂ is 25 and the dielectric constant of ZrO ₂ is 25, and the HfZrO nanocomposite dielectric film, which is a nanocomposite material of HfO ₂ and ZrO ₂ , is measured at 25 levels. have.

According to the results shown in Figure 6, HfZrO nanocomposite dielectric layer is excellent, yet bring the value of the same level as the dielectric 25 of HfO ₂ ensure a high dielectric constant Here the nanocomposite dielectric layer gets no dielectric loss of HfO ₂ leakage current characteristics.

On the other hand, after depositing the HfZrO nanocomposite dielectric film, subsequent annealing is involved to effectively remove organic matter contained in the film and to densify the film. At this time, the annealing process is carried out for 30 seconds to 120 seconds at 300 ℃ to 500 ℃ temperature in O ₃ atmosphere.

7 is a view for explaining the atomic layer deposition method of the HfLaO nanocomposite dielectric film according to the second embodiment of the present invention, the concept of supplying a gas into the chamber when the HfLaO nanocomposite dielectric film is formed by the atomic layer deposition method. to be.

The unit cycle of the atomic layer deposition process for depositing the HfLaO nanocomposite dielectric film is as follows.

[Unit cycle 2]

[(Hf source / purge / oxidant exposure / purge) _y (La source / purge / oxidant exposure / purge) _z ] _n

In unit cycle 2, the Hf source is a pulse supplying an Hf source for forming HfO ₂ , the La source is a pulse for supplying a La source for forming La ₂ O ₃ , and y determines a film thickness of HfO ₂ . Number of cycles (Hf source / purge / oxidant exposure / purge), z denotes the number of cycles (La source / purge / oxidant exposure / purge) to determine the film thickness of La ₂ O ₃ , and n denotes the number of cycles of HfLaO dielectric film. The number of cycles for determining the thickness is shown.

Looking at unit cycle 2 in detail, the (Hf source / purge / oxidant exposure / purge) _y cycle refers to the HfO ₂ deposition cycle that repeats the cycle consisting of Hf source, purge, oxidant exposure, and purge y times (La source / Purge / Oxidant Exposure / Purge) The _z cycle refers to a La ₂ O ₃ deposition cycle that repeats _z cycles of La source, purge, oxidant exposure and purge. By repeating each deposition cycle as described above y and z times, HfO ₂ and La ₂ O ₃ of the required thickness are deposited respectively, and the integrated deposition cycle of HfO ₂ deposition cycle and La ₂ O ₃ deposition cycle is repeated n times. To determine the total thickness of the HfLaO nanocomposite dielectric film.

Referring to FIG. 7, a deposition example of an HfLaO nanocomposite dielectric film is described in detail.

Before describing the deposition process, the HfO ₂ deposition cycle is (Hf / N ₂ / O ₃ / N ₂ ) as a unit cycle and the unit cycle is repeated y times. In the unit cycle, Hf is an Hf source, N ₂ is a purge gas, and O ₃ is an oxidant gas.

In the La ₂ O ₃ deposition cycle, (La / N ₂ / O ₃ / N ₂ ) is a unit cycle, and the unit cycle is repeated z times. In the unit cycle, La is a La source, N ₂ is a purge gas, and O ₃ is an oxidant gas.

The HfO ₂ deposition cycle and the La ₂ O ₃ deposition cycle proceed in a chamber maintaining a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C.

First, the deposition of HfO ₂ will be described. After vaporizing an Hf source selected from HfCl ₄ , Hf (NO ₃ ) ₄ , Hf (NCH ₂ C ₂ H ₅ ) _4, or Hf (OC ₂ H ₅ ) ₄ in a vaporizer, The Hf source is adsorbed by flowing 0.1 seconds to 3 seconds into a chamber that maintains a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove the unreacted Hf source, and the adsorbed Hf source and O are flowed by oxidizing O ₃ gas for 0.1 seconds to 3 seconds. Induce a reaction between ₃ to deposit HfO ₂ . Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted O ₃ and the reaction byproduct.

Cycloalkyl Hf source, N ₂ purge, O ₃ supplied, N units of the _second purge process as described above, and subjected to a cycle unit of y-repeated to deposit a desired thickness of HfO ₂ (1Å~5Å). As the oxidant, H ₂ O vapor may be used in addition to O ₃ , and an inert gas such as argon (Ar) may be used in addition to nitrogen (N ₂ ) as the purge gas.

Next, La ₂ O ₃ deposition will be described. La (tmhd) ₃ , which is a La source, is kept in the chamber for 0.1 seconds to 3 seconds while the substrate temperature is maintained at 100 ° C. to 450 ° C. and the pressure is 0.1 to 10 tor. Flow to adsorb La (tmhd) ₃ to the substrate. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted La (tmhd) ₃ , and the O ₃ gas, which is an oxidant, is flowed for 0.1 seconds to 3 seconds, to adsorb La. The reaction between (tmhd) ₃ and O ₃ is induced to deposit La ₂ O ₃ in atomic layer units. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted O ₃ and the reaction byproduct.

La (tmhd) ₃ supplied as described above, N ₂ purge, O ₃ supplied, the process cycles of N ₂ purge unit, and this unit cycle z times repeatedly performed by La ₂ O ₃ of desired thickness (1Å~5Å) Deposit. Here, the La source of the La ₂ O ₃ in addition to _three aforementioned La (tmhd) La (iPrCp) 3, La (tmhd) 3: tetraglyme, La (tmhd) 3: tetraen or La (tmhd) _3: selected from diglyme You can also use La sauce. In addition to O ₃ , H ₂ O vapor may be used as the oxidant, and inert gas such as argon (Ar) may be used as the purge gas.

FIG. 8 is a diagram illustrating the structure of the HfLaO nanocomposite dielectric film deposited by FIG. 7.

Referring to FIG. 8, the HfLaO nanocomposite dielectric layer is not formed by stacking HfO ₂ and La ₂ O ₃ in a layer by layer concept, but a mixture of HfO ₂ and La ₂ O ₃ in a nanocomposite form. Has

The reason for having such a mixed structure in the form of nanocomposite is because HfO ₂ and La ₂ O ₃ are deposited using the atomic layer deposition method of FIG. 7, in particular, the number of HfO ₂ deposition cycles and the number of La ₂ O ₃ deposition cycles are controlled. This is because HfO ₂ and La ₂ O ₃ are formed to have a thickness of 1 kPa to 5 kPa, respectively. Here, the thickness of 1Å to 5Å of HfO ₂ and La ₂ O ₃ is the thickness that each film is formed discontinuously, and when deposited thicker than 5Å, HfO ₂ and La ₂ O ₃ are layered by layer. It becomes a structure laminated | stacked in the form.

In order to form the HfLaO nanocomposite dielectric film in which HfO ₂ and La ₂ O ₃ are mixed using the atomic layer deposition method, the following conditions must be satisfied.

First, in order to increase the nano-composite effect of HfO ₂ and La ₂ O ₃ (Hf source / purge / oxidant exposure / purge), HfO ₂ and (La source / purge / oxidant exposure) formed by _y cycles. / Purge) The thickness of La ₂ O ₃ formed by the _z cycle is 1 kPa to 5 kPa. In this case, when the thickness of each film is thicker than 5 GPa, each film exhibits an independent characteristic-continuous film- and thus may exhibit the same or deteriorated characteristics as the conventional HfO ₂ / La ₂ O ₃ laminated dielectric film.

Secondly, for the nano-composite structure where HfO ₂ and La ₂ O ₃ are mixed, not the concept of layer by layer, the (Hf source / purge / oxidant exposure / purge) _y cycle and (La source / Purge / oxidant exposure / purge) The number of cycles y and z in the _z cycle is 10 or less. In other words, the ratio y: z is set to 1:10 to 10: 1.

As above, when y and z are 10 or less, HfO ₂ and La ₂ O ₃ are not laminated but form a nanocomposite that is mixed, thereby forming a new composite that is neither La ₂ O ₃ nor HfO ₂ . HfLaO nanocomposite dielectric film is formed. In addition, when the ratio of y: z, which is the deposition cycle ratio, is set to 1:10 to 10: 1, HfO ₂ and La ₂ O ₃ can be deposited at a thickness of 1 kPa to 5 kPa, respectively.

As described above, when the HfLaO nanocomposite dielectric film is deposited with a thickness of 1 Å to 5 각각 by controlling the deposition cycle ratio (y: z = 1: 10 to 10: 1) through atomic layer deposition, the mixture is deposited in nanocomposite form. Compared to HfO ₂ , La ₂ O ₃ or HfO ₂ / La ₂ O ₃ laminated film, the crystallization temperature is higher, and it can withstand high temperatures, and the dielectric properties are excellent. Here, the improvement of the dielectric characteristic of the dielectric constant because the dielectric constant of HfO ₂ is 25 and the dielectric constant is 30, the La ₂ O ₃ HfLaO nanocomposite dielectric layer can be seen from 25 to 30 to be greater than the level of dielectric constant of at least HfO _2.

On the other hand, after depositing the HfLaO nanocomposite dielectric film, subsequent annealing is involved to effectively remove organic matter contained in the film and to densify the film. At this time, the annealing process is carried out for 30 seconds to 120 seconds at 300 ℃ to 500 ℃ temperature in O ₃ atmosphere.

9 is a view for explaining the atomic layer deposition method of the HfTaO nanocomposite dielectric film according to the third embodiment of the present invention, the concept of supplying a gas into the chamber when the HfTaO nanocomposite dielectric film is formed by the atomic layer deposition method. to be.

The unit cycle of the atomic layer deposition process for depositing an HfTaO nanocomposite dielectric film is as follows.

[Unit Cycle 3]

[(Hf source / purge / oxidant exposure / purge) _y (Ta source / purge / oxidant exposure / purge) _z ] _n

In unit cycle 3, the Hf source is a pulse supplying an Hf source for forming HfO ₂ , the Ta source is a pulse supplying a Ta source for forming Ta ₂ O ₅ , and y is a film thickness of HfO ₂ . The number of cycles (Hf source / purge / oxidant exposure / purge), z denotes the number of cycles (Ta source / purge / oxidant exposure / purge) to determine the film thickness of Ta ₂ O ₅ , and n is the number of cycles of HfTaO dielectric film. The number of cycles for determining the thickness is shown.

Looking at unit cycle 3 in detail, the (Hf source / purge / oxidant exposure / purge) _y cycle refers to the HfO ₂ deposition cycle that repeats the cycle consisting of Hf source, purge, oxidant exposure and purge y times (Ta source / Purge / Oxidant Exposure / Purge) The _z cycle refers to a Ta ₂ O ₅ deposition cycle that repeats z cycles consisting of Ta source, purge, oxidant exposure and purge. By repeating each of the above deposition cycles y and z times, HfO ₂ and Ta ₂ O ₅ of the required thickness are deposited respectively, and the integrated deposition cycle of HfO ₂ deposition cycle and Ta ₂ O ₅ deposition cycle is repeated n times. To determine the total thickness of the HfTaO nanocomposite dielectric film.

The deposition example of the HfZrO nanocomposite dielectric film will be described in detail with reference to FIG. 4.

Before describing the deposition process, the HfO ₂ deposition cycle is (Hf / N ₂ / O ₃ / N ₂ ) as a unit cycle and the unit cycle is repeated y times. In the unit cycle, Hf is an Hf source, N ₂ is a purge gas, and O ₃ is an oxidant gas.

In the Ta ₂ O ₅ deposition cycle, (Ta / N ₂ / O ₃ / N ₂ ) is a unit cycle, and the unit cycle is repeated z times. In the unit cycle, Ta is a Ta source, N ₂ is a purge gas, and O ₃ is an oxidant gas.

The HfO ₂ deposition cycle and the Ta ₂ O ₅ deposition cycle proceed in a chamber maintaining a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C.

First, the deposition of HfO ₂ will be described. After vaporizing an Hf source selected from HfCl ₄ , Hf (NO ₃ ) ₄ , Hf (NCH ₂ C ₂ H ₅ ) _4, or Hf (OC ₂ H ₅ ) ₄ in a vaporizer, The Hf source is adsorbed by flowing 0.1 seconds to 3 seconds into a chamber that maintains a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove the unreacted Hf source, and the adsorbed Hf source and O are flowed by oxidizing O ₃ gas for 0.1 seconds to 3 seconds. Induce a reaction between ₃ to deposit HfO ₂ . Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted O ₃ and the reaction byproduct.

Cycloalkyl Hf source, N ₂ purge, O ₃ supplied, N units of the _second purge process as described above, and subjected to a cycle unit of y-repeated to deposit a desired thickness of HfO ₂ (1Å~5Å). As the oxidant, H ₂ O vapor may be used in addition to O ₃ , and an inert gas such as argon (Ar) may be used in addition to nitrogen (N ₂ ) as the purge gas.

Next, Ta ₂ O ₅ deposition will be described. Ta pentoxide is flowed into the chamber for 0.1 to 3 seconds while the substrate temperature is maintained at 100 ° C. to 450 ° C. and the pressure is 0.1 to 10 tor. To adsorb Ta pentoxide to the substrate. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted Ta pentoxide, and the adsorbed Ta pentoxide is flowed by oxidizing O ₃ gas for 0.1 seconds to 3 seconds. The reaction between and O ₃ is induced to deposit Ta ₂ O ₅ in atomic layer units. Next, a purge process is performed in which nitrogen (N ₂ ) gas is flowed for 0.1 seconds to 5 seconds to remove unreacted O ₃ and the reaction byproduct.

The Ta pentoside supply, the N ₂ purge, the O ₃ feed, and the N ₂ purge as described above are used as a unit cycle, and the unit cycle is repeated z times to deposit Ta ₂ O ₅ having a desired thickness ( ₁ to ₅ μs). do. Here, as an oxidant, H ₂ O vapor may be used in addition to O ₃ , and an inert gas such as argon (Ar) may be used as the purge gas.

FIG. 10 is a diagram illustrating the structure of the HfTaO nanocomposite dielectric film deposited by FIG. 9.

Referring to FIG. 10, the HfTaO nanocomposite dielectric layer is not formed by stacking HfO ₂ and Ta ₂ O ₅ in a layer by layer concept, but a mixture of HfO ₂ and Ta ₂ O ₅ in a nanocomposite form. Has

The reason for having the mixed structure in the form of nanocomposite is because HfO ₂ and Ta ₂ O ₅ are deposited by using the atomic layer deposition method of FIG. 9, in particular, the number of HfO ₂ deposition cycles and the number of Ta ₂ O ₅ deposition cycles are controlled. This is because HfO ₂ and Ta ₂ O ₅ are formed to have a thickness of 1 kPa to ₅ kPa, respectively. Here, the thickness of 1Å to 5Å of HfO ₂ and Ta ₂ O ₅ is the thickness of each film formed discontinuously, and when deposited thicker than 5Å, HfO ₂ and Ta ₂ O ₅ are layered by layer. It becomes a structure laminated | stacked in the form.

In order to form the HfTaO nanocomposite dielectric film in which HfO ₂ and Ta ₂ O ₅ are mixed by using the atomic layer deposition method, the following conditions must be satisfied.

First, HfO ₂ and Ta ₂ O ₅ nanocomposite (Nano-composite) to increase the effect (Hf source / purge / oxidant exposure / purge) HfO ₂ and (Ta source / purge / oxidant exposure formed by the _y-cycle of / Purge) The thickness of Ta ₂ O ₅ formed by the _z cycle is set to be 1 kPa to ₅ kPa. In this case, when the thickness of each film is thicker than 5 GPa, each film exhibits an independent characteristic-continuous film- and thus may exhibit the same or deteriorated characteristics as the conventional HfO ₂ / Ta ₂ O ₅ laminated dielectric film.

Second, for the nano-composite structure where HfO ₂ and Ta ₂ O ₅ are mixed, not the concept of layer by layer, the (Hf source / purge / oxidant exposure / purge) _y cycle and (Ta source) / Purge / oxidant exposure / purge) The number of cycles y and z in the _z cycle is 10 or less. In other words, the ratio y: z is set to 1:10 to 10: 1.

As above, when y and z are 10 or less, HfO ₂ and Ta ₂ O ₅ are not laminated but form a mixed nanocomposite, thereby creating a new composite which is neither Ta ₂ O ₅ nor HfO ₂ . HfTaO nanocomposite dielectric film is formed. In addition, when the ratio of y: z, which is the deposition cycle ratio, is set to 1:10 to 10: 1, HfO ₂ and Ta ₂ O ₅ can be deposited at a thickness of 1 kPa to ₅ kPa, respectively.

As described above, when the HfTaO nanocomposite dielectric film is deposited to a thickness of 1 Å to 5 각각 by controlling the deposition cycle ratio (y: z = 1: 10 to 10: 1) through atomic layer deposition, mixed and deposited in nanocomposite form Compared to the HfO ₂ , Ta ₂ O ₅ or HfO ₂ / Ta ₂ O ₅ laminated film, the crystallization temperature is higher, and it can withstand high temperatures, and the dielectric properties are excellent. In this case, the dielectric constant is improved because the dielectric constant of HfO ₂ is 25 and the dielectric constant of Ta ₂ O ₅ is 26, indicating that the dielectric constant of the HfTaO nanocomposite dielectric film is at least higher than that of HfO ₂ .

On the other hand, after the deposition of the HfTaO nanocomposite dielectric film, subsequent annealing is involved to effectively remove organic matter contained in the film and to densify the film. At this time, the annealing process is carried out for 30 seconds to 120 seconds at 300 ℃ to 500 ℃ temperature in O ₃ atmosphere.

The HfZrO, HfLaO, and HfTaO nanocomposite dielectric films according to the first to third embodiments described above have a total thickness of 25 kPa to 200 kPa.

FIG. 11 shows the structure of a capacitor employing the HfZrO nanocomposite dielectric film of the present invention.

Referring to FIG. 11, the capacitor of the present invention includes a HfZrO nanocomposite dielectric layer 22 and a HfZrO nanocomposite dielectric layer in which HfO ₂ and ZrO ₂ are mixed in a nanocomposite form on the lower electrode 21 and the lower electrode 21. It consists of the upper electrode 23 on 22. As shown in FIG.

In FIG. 11, the lower electrode 21 and the upper electrode 23 are selected from the group consisting of a polysilicon film doped with phosphorus (P) or arsenic (As), TiN, Ru, RuO ₂ , Pt, Ir, and IrO ₂ . For example, the lower electrode 21 and the upper electrode 23 are both made of a polysilicon film to form a silicon insulator silicon (SIS) capacitor structure, or the lower electrode 21 is a polysilicon film and the upper electrode 23. ) Is composed of a metal film or a metal oxide film to form a metal insulator silicon (MIS) capacitor structure, or the lower electrode 21 and the upper electrode 23 are all composed of a metal film or a metal oxide film, and thus a metal insulator metal (MIM) capacitor The structure can be formed. In addition, the lower electrode 21 may be a three-dimensional structure of a stack structure, a concave structure, or a cylinder structure.

The HfZrO nanocomposite dielectric layer 22 disposed between the lower electrode 21 and the upper electrode 23 is deposited by atomic layer deposition (ALD) using the principles of FIGS. 4 and 5. As shown in Unit Cycle 1, the cycle of depositing HfO ₂ in atomic layer units and the cycle of depositing ZrO ₂ in atomic layer units are repeated to form a total thickness of 25 kPa to 200 kPa.

In the above HfZrO nanocomposite dielectric layer 22, lower electrode 21 and the film is in direct contact to the top electrode (23), HfO ₂ and ZrO ₂ is not a single HfO ₂ and ZrO ₂ are both the lower electrode 21 and upper electrode It has a form in direct contact with 23 (see Fig. 5). That is, the HfZrO nanocomposite dielectric layer 22 is not formed of HfO ₂ and ZrO ₂ in a stack form of a layer by layer concept, but HfO ₂ and ZrO ₂ are mixed in a nanocomposite form.

As described above, the HfZrO nanocomposite dielectric film 22 in which HfO ₂ and ZrO ₂ are mixed in the form of a nanocomposite is deposited by atomic layer deposition. That is, as described with reference to FIG. 5, since the film can be formed discontinuously according to the cycle number adjustment due to the characteristics of the atomic layer deposition method, HfO ₂ and ZrO ₂ are mixed in the form of nanocomposite.

The atomic layer deposition method of the HfZrO nanocomposite dielectric layer 22 will be described with reference to FIGS. 4 and 5 and the description thereof.

The HfZrO nanocomposite dielectric film 22 is deposited using atomic layer deposition (ALD), wherein the number of cycles is adjusted so that the thicknesses of HfO ₂ and ZrO ₂ are 1 kPa to 5 kPa, respectively, and the HfZrO nanocomposite dielectric film 22 ) Should be 25 총 to 200Å thick. In the description of FIGS. 4 and 5, the ratio of y: z, which is the ratio of the number of cycles, is set to be 1:10 to 10: 1.

Here, the thickness of 1Å to 5Å of HfO ₂ and ZrO ₂ is a thickness in which each film is formed discontinuously. In case of depositing thicker than 5Å, it has a continuous film form and is directly connected to the lower electrode 21 and the upper electrode 23. It becomes a laminated structure of HfO ₂ (22a) and ZrO ₂ (22b) that are not in contact with each other, resulting in deterioration in characteristics than the HfZrO nanocomposite dielectric film.

Meanwhile, in FIG. 11, when the lower electrode 21 is a polysilicon film, when the HfZrO nanocomposite dielectric film 22 is formed on the surface of the lower electrode 21, the surface of the lower electrode 21 is oxidized to form a natural oxide film. In order to suppress this, a silicon nitride film (SiN, 24) is formed by performing a rapid thermal process (RTP) for 10 seconds to 120 seconds at a temperature of 800 ° C. to 1000 ° C. in an NH ₃ atmosphere. As such, forming the silicon nitride film 24 prevents a decrease in the leakage current characteristic and a decrease in the dielectric constant caused by the formation of the natural oxide film.

In FIG. 11, the case where the dielectric film of the capacitor is an HfZrO nanocomposite dielectric film has been described. However, HfLaO and HfTaO may be applied to the dielectric film of the capacitor.

As described above, by using HfZrO, HfLaO, or HfTaO having a nanocomposite shape as the dielectric film of the capacitor, leakage current characteristics can be secured even at a thin thickness, thereby obtaining high charge capacity.

Although the technical idea of the present invention has been described in detail according to the above preferred embodiment, it should be noted that the above-described embodiment is for the purpose of description and not of limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention.

The present invention described above has the effect of manufacturing a capacitor having a high dielectric constant while ensuring a leakage current characteristics without loss of dielectric constant even in a relatively thin thickness by adopting a nano-composite dielectric film.

Claims (43)

A nanocomposite dielectric film in which a dielectric film having a dielectric constant at least equal to that of HfO ₂ and at least the HfO ₂ is mixed in a nanocomposite form The dielectric film of the capacitor comprising a. The method of claim 1, The dielectric film has a dielectric constant of 25 to 30 and a bandgap energy of 4.3 to 7.8. The method of claim 1, The dielectric film is a dielectric film of a capacitor, characterized in that selected from ZrO ₂ , La ₂ O ₃ or Ta ₂ O ₅ . The method according to any one of claims 1 to 3, The nanocomposite dielectric film is a capacitor dielectric film, characterized in that the HfO ₂ and the dielectric film are each mixed with a thickness of 1 ~ 5 Å per deposition cycle through the atomic layer deposition method. The method of claim 4, wherein The nanocomposite dielectric film has a thickness of 25 kV to 200 kV. Depositing a nanocomposite dielectric film in which HfO ₂ and the dielectric film are mixed in a nanocomposite form by repeating the [HfO ₂ deposition cycle] and the [dielectric film deposition cycle] y and z times using atomic layer deposition; And Annealing step for densification of the nanocomposite dielectric layer Dielectric film production method of a capacitor comprising a. The method of claim 6, [HfO ₂ deposition cycle], Adsorbing an Hf source; A purge step to remove unreacted Hf source from the Hf source; Supplying an oxidant to induce a reaction with the adsorbed Hf source to deposit HfO ₂ ; And Purge step to remove unreacted oxidants and reaction byproducts Dielectric film production method of a capacitor comprising a. The method of claim 7, wherein [HfO ₂ deposition cycle], A method for producing a dielectric film for a capacitor, characterized by advancing at a pressure of 0.1 tortor to 10torr and a substrate temperature of 100 to 450C. The method of claim 7, wherein Adsorbing the Hf source, The Hf source selected from HfCl ₄ , Hf (NO ₃ ) ₄ , Hf (NCH ₂ C ₂ H ₅ ) _4, or Hf (OC ₂ H ₅ ) ₄ is vaporized in a vaporizer, and the pressure is from 0.1 to 10 tor and at a temperature of from 100 to A method of manufacturing a dielectric film for a capacitor, characterized by flowing 0.1 seconds to 3 seconds into a chamber maintaining a substrate temperature of 450 ° C. The method of claim 7, wherein The supply of the oxidant, A method for producing a dielectric film for a capacitor, characterized by flowing O ₃ or H ₂ O vapor for 0.1 to 5 seconds. The method of claim 7, wherein The purge step, A method of producing a dielectric film for a capacitor, characterized by advancing for 0.1 to 3 seconds using nitrogen or an inert gas. The method of claim 6, The dielectric film deposited by the [dielectric film deposition cycle], ZrO ₂ , La ₂ O ₃ or Ta ₂ O _{5 A} method for producing a dielectric film of a capacitor, characterized in that. The method of claim 12, Zr source for ZrO ₂ deposited by the [dielectric film deposition cycle], A method for producing a dielectric film for a capacitor, comprising using TEMAZ [Zr {N (CH ₃ ) (C ₂ H ₅ )} ₄ ] or TDEAZ [Zr {N (C ₂ H ₅ ) ₂ } ₄ ]. The method of claim 12, La source for La ₂ O ₃ deposited by the [dielectric film deposition cycle], La (tmhd) ₃ , La (iPrCp) ₃ , La (tmhd) ₃ : tetraglyme, La (tmhd) ₃ : tetraen or La (tmhd) ₃ : a method for producing a dielectric film of a capacitor, characterized in that didigmeme. The method of claim 12, Ta source for Ta ₂ O ₅ deposited by the [dielectric film deposition cycle], Method for producing a dielectric film of a capacitor, characterized in that it uses Ta pentoxide. The method according to any one of claims 6 to 15, The ratio of y and z is 1:10 to 10: 1, characterized in that the dielectric film manufacturing method of the capacitor. The method according to any one of claims 6 to 15, The HfO ₂ and the dielectric film are each deposited several times at a thickness of 1 ~ 5Å per deposition cycle so that the nanocomposite dielectric film has a thickness of 25 ~ 200Å thickness and mixed in the form of nanocomposite. The method of claim 6, The annealing step, A method of producing a dielectric film for a capacitor, characterized in that the heat treatment for 30 seconds to 120 seconds at a temperature of 300 ℃ to 500 ℃. Lower electrode; Nanocomposite dielectric layer is dielectric layer having the same dielectric constant and at least a dielectric constant of the HfO ₂ and HfO ₂ on the lower electrode is formed of a mixture to form a nanocomposite; And An upper electrode on the nanocomposite dielectric layer Capacitor comprising a. The method of claim 19, And the HfO ₂ and the dielectric film forming the nanocomposite dielectric film are deposited by atomic layer deposition. The method of claim 20, The nanocomposite dielectric film, The capacitor and the HfO ₂ and the dielectric film each having a thickness of 1Å ~ 5Å deposited several times to have a nano-composite form. The method of claim 19, The nanocomposite dielectric film has a thickness of 25 kPa to 200 kPa. The method according to any one of claims 19 to 22, The dielectric film, A capacitor, characterized in that selected from ZrO ₂ , La ₂ O ₃ or Ta ₂ O ₅ . The method of claim 23, wherein The lower electrode and the upper electrode, A capacitor characterized in that the polysilicon film doped with phosphorous or arsenic. The method of claim 24, And a silicon nitride film formed between the lower electrode and the nanocomposite dielectric film. The method of claim 23, wherein The lower electrode and the upper electrode, A capacitor, characterized in that selected from TiN, Ru, RuO ₂ , Pt, Ir or IrO ₂ . Forming a lower electrode; Depositing a nanocomposite dielectric film in which a dielectric film having a dielectric constant at least equal to that of HfO ₂ and at least the HfO ₂ is mixed in a nanocomposite form by using an atomic layer deposition method on the lower electrode; Annealing for densification of the nanocomposite dielectric film; And Forming an upper electrode on the annealed nanocomposite dielectric layer Method of manufacturing a capacitor comprising a. The method of claim 27, Depositing the nanocomposite dielectric film, [HfO ₂ deposition cycle] and a method for manufacturing a capacitor, characterized in that the dielectric layer - dielectric layer deposition cycle; for depositing each of y times and proceeds z iterations for using atomic layer deposition to deposit the HfO _2. The method of claim 28, [HfO ₂ deposition cycle], Adsorbing an Hf source; A purge step to remove unreacted Hf source from the Hf source; Supplying an oxidant to induce a reaction with the adsorbed Hf source to deposit HfO ₂ ; And Purge step to remove unreacted oxidants and reaction byproducts Method of manufacturing a capacitor comprising a. The method of claim 29, [HfO ₂ deposition cycle], A process for producing a capacitor, characterized by advancing at a pressure of 0.1torr to 10torr and a substrate temperature of 100 ° C to 450 ° C. The method of claim 29, Adsorbing the Hf source, The Hf source selected from HfCl ₄ , Hf (NO ₃ ) ₄ , Hf (NCH ₂ C ₂ H ₅ ) _4, or Hf (OC ₂ H ₅ ) ₄ is vaporized in a vaporizer, and the pressure is from 0.1 to 10 tor and at a temperature of from 100 to A method for producing a capacitor, characterized by flowing for 0.1 seconds to 3 seconds into the chamber maintaining the substrate temperature of 450 ℃. The method of claim 29, The supply of the oxidant, A process for producing a capacitor, characterized by flowing O ₃ or H ₂ O steam for 0.1 to 5 seconds. The method of claim 29, The purge step, A method for producing a capacitor, characterized by advancing for 0.1 to 3 seconds using nitrogen or an inert gas. The method of claim 28, The dielectric film deposited by the [dielectric film deposition cycle], ZrO ₂ , La ₂ O ₃ or Ta ₂ O _{5 A} method for producing a capacitor, characterized in that. The method of claim 34, wherein Zr source for ZrO ₂ deposited by the [dielectric film deposition cycle], A process for producing a capacitor, characterized by using TEMAZ [Zr {N (CH ₃ ) (C ₂ H ₅ )} ₄ ] or TDEAZ [Zr {N (C ₂ H ₅ ) ₂ } ₄ ]. The method of claim 34, wherein La source for La ₂ O ₃ deposited by the [dielectric film deposition cycle], La (tmhd) ₃ , La (iPrCp) ₃ , La (tmhd) ₃ : tetraglyme, La (tmhd) ₃ : tetraen or La (tmhd) ₃ : diglyme. The method of claim 34, wherein Ta source for Ta ₂ O ₅ deposited by the [dielectric film deposition cycle], Method for producing a capacitor, characterized by using Ta pentoxide. The method of claim 28, The ratio of y and z is 1: 10-10: 1, The manufacturing method of a capacitor characterized by the above-mentioned. The method according to any one of claims 27 to 38, The HfO ₂ and the dielectric film is deposited several times at a thickness of 1 kW to 5 kW per deposition cycle so that the nanocomposite dielectric film has a thickness of 25 kPa to 200 kPa, and is mixed in a nanocomposite form. The method of claim 27, The annealing step, A method for producing a capacitor, characterized in that the heat treatment for 30 seconds to 120 seconds at 300 ℃ to 500 ℃ temperature. The method of claim 27, The lower electrode, A process for producing a capacitor, characterized in that it is formed of a polysilicon film doped with phosphorus or arsenic. The method of claim 41, wherein And forming a silicon nitride film between the lower electrode and the nanocomposite dielectric film. The method of claim 42, wherein The silicon nitride film, And forming a surface of the lower electrode by RTP at a temperature of 800 ° C. to 1000 ° C. for 10 seconds to 120 seconds in an NH ₃ atmosphere.

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