KR20010097641A - Capacitor of semiconductor memory device and the manufacturing method thereof - Google Patents

Abstract

Disclosed are a capacitor of a semiconductor memory device and a method of manufacturing the same. The disclosed method of manufacturing the capacitor are laminated one by as much as the critical thickness of structural phase transition of BaSrTiO ₃ (BST) thin film SrTiO ₃ (STO) and BaTiO and the ₃ (BTO) continuously deposited alternately by atomic layer unit, each interlayer takes place A dielectric film of a capacitor having a high dielectric constant is formed.

In depositing the SrTiO ₃ and BaTiO ₃ dielectric films, each dielectric film is deposited on an atomic layer basis by digital chemical vapor deposition without depending on a conventional chemical vapor deposition (CVD) method or a sputtering deposition method.

According to the present invention, by continuously depositing STO and BTO, not only can control the atomic layer thickness and obtain a uniform thin film, but also can induce lattice deformation, thereby obtaining a dielectric film having a high dielectric constant. In addition, by depositing the STO and BTO continuously, it can be controlled by the cycle of sending the reactant using the principle of depositing the capacitor dielectric film thickness thinner in the high-integration device one atomic layer per cycle.

Description

Capacitor of semiconductor memory device and manufacturing method thereof

The present invention relates to a capacitor of a semiconductor memory device and a method of manufacturing the same, and more particularly, to a capacitor having a high dielectric constant and a method of manufacturing the same.

The unit element of the DRAM (Dynamic Random Access Memory), which is one of the semiconductor memory elements, is composed of one transistor and an information storage capacitor. The storage capacity of the information storage capacitor should be at least 30 × 10 ^-15 F / unit cell in order to prevent malfunction due to α-particles or the like.

As DRAMs become more integrated, methods for securing sufficient capacitance in a smaller area include (1) increasing the effective cross-sectional area of the capacitor, (2) reducing the thickness of the dielectric thin film, and (3) using materials with large dielectric constants. How to use, etc.

In general, capacitance is increased by stacking and trenching structures having a three-dimensional structure capable of ultra-thinning dielectric materials such as SiO ₂ in the capacitor or effectively increasing the effective structure of the capacitor structure.

Capacitors with three-dimensional structure have the advantage of being able to expand capacitance most effectively, while requiring complex manufacturing processes and high manufacturing costs. Three-dimensional structures to increase the degree of integration include stack, trench, pin and cylinder capacitors, and manufacturing process limitations are exposed around 256M DRAM. In trench-type capacitors, as integration increases, leakage currents between trenches cause problems, and stacked and fin-type and cylindrical cells form severe bends and steps on the surface to achieve large capacitances, making photo-etching of subsequent processes difficult and thinner. The low mechanical strength of the pin or cylinder adds to the difficulty of the process.

In the case of a capacitor with a thinned dielectric layer, when the thickness of the SiO ₂ thin film applied as the dielectric material becomes thinner than 100 mW, the so-called Fowler-Nordheim current lowers the reliability of the thin film and thus the large capacity. It is difficult to apply as a memory device.

The capacitor using a high dielectric constant material is a ferroelectric material, and is a type of ferroelectric random access memory (FRAM). Ferroelectric materials have spontaneous polarization below the Curie temperature and have a dielectric constant of several hundred to 1000, and are characterized by spontaneous polarization even when an electric field is not applied. Such a ferroelectric material has an equivalent oxide thickness of 10 μs or less even though it has a thickness of about several hundred μs, thereby exhibiting an effect equivalent to that of a dielectric film having an oxide thickness of 10 μs or less.

Among the ferroelectric materials used in DRAM, BST (BaSrTiO ₃ ), which has a crystal structure called perovskite type, can maintain a high dielectric constant even at high frequencies compared to PZT and SBT (Sr _x Bi _y TiO _z ), and appropriate Ba / Sr Since it is converted into a phase dielectric according to the ratio, it is excellent in characteristics such as fatigue and aging, and thus, it has been spotlighted as a dielectric material of a capacitor for DRAM. However, since the ferroelectric material requires a high temperature at the time of deposition, there is a disadvantage in that interdiffusion (diffusion) occurs between the electrode at the time of deposition or heat treatment to generate another oxide to reduce the capacity of the capacitor.

1 is a schematic cross-sectional view of a conventional capacitor to which the ferroelectric material is applied. Upper and lower electrodes made of platinum (Pt) are provided above and below the BST thin film. In some cases, a diffusion barrier may be positioned on the lower electrode. In such a capacitor, a thin film by a high dielectric constant material such as BST is formed by a sputtering method, a metal-organic chemical vapor deposition method, a spin coating method, or the like.

Deposition by sputtering is a method that generates plasma and removes ions in the target and deposits them on the substrate, which is advantageous in the purity and adhesion of thin films, but it is difficult to secure uniformity in irregularities. Because of this, the main cause of leakage current in the side of the electrode is known, the application is very limited in the fine pattern.

The organometallic chemical vapor deposition technique is a technique that is commonly used to inject a variety of gases and to deposit gases on the substrate by inducing the reaction of the gases using energy such as heat, light and plasma. In the chemical vapor deposition method, the chemical reaction rate is controlled by heat, light, plasma, or the like, which supplies reaction energy, or by the amount and ratio of gas. However, these chemical reactions generally occur very quickly and are difficult to control to deposit with the thermodynamic stability of the atoms. Therefore, the physical, electrical, chemical properties, etc. of the thin film has a disadvantage compared to the atomic layer deposition method, it is difficult to ensure the uniformity of the thin film in minute unevenness. In addition, since the increase in the degree of integration of semiconductor devices requires a higher aspect ratio, the demand for thin film uniformity in unevenness is intensifying.

It is a first object of the present invention to provide a capacitor of a semiconductor device capable of coping with high integration in a semiconductor device by having a high dielectric constant, and a method of manufacturing the same.

A second object of the present invention is to provide a capacitor of a semiconductor device having excellent electrical and physical properties and a method of manufacturing the same.

It is a third object of the present invention to provide a capacitor of a semiconductor device having a uniform dielectric thin film even at a high aspect ratio and a method of manufacturing the same.

1 is a schematic cross-sectional view of a semiconductor memory device to which a capacitor using a conventional high dielectric material is applied.

2A shows the crystal structure of the phase dielectric BST.

2b shows the crystal structure of the steel dielectric BST.

3 is a graph of lattice constant change in SrTiO3-BaTiO3 system.

Figure 4a is a flow chart of the first type of STO thin film forming step in the capacitor manufacturing method according to the present invention.

Figure 4b is a flow chart of the first type of BTO thin film forming step in the capacitor manufacturing method according to the present invention.

5A is a flowchart of a second type STO thin film forming step in the method of manufacturing a capacitor according to the present invention.

5B is a flowchart of the second type of BTO thin film forming step in the capacitor manufacturing method according to the present invention.

6A is a flowchart of a third type STO thin film forming step in the capacitor manufacturing method according to the present invention.

6B is a flowchart of the third type of BTO thin film forming step in the capacitor manufacturing method according to the present invention.

7A is a flow chart of a first embodiment of a capacitor manufacturing method according to the present invention.

7B is a flow chart of a second embodiment of a capacitor manufacturing method according to the present invention.

8 is a schematic cross-sectional view of a semiconductor memory device to which an embodiment of a capacitor according to the present invention is applied.

9 is a schematic cross-sectional view of a semiconductor memory device to which another embodiment of a capacitor according to the present invention is applied.

According to the present invention to achieve the above object,

A capacitor of a semiconductor memory device comprising a dielectric film and upper and lower electrodes positioned above and below the dielectric film.

The dielectric film is composed of a multi-layered structure composed of alternating atomic layer unit thicknesses of STO thin film and BTO thin film, and the dielectric film has a thickness in which phase transition due to naturally occurring strain is generated. A capacitor of the device is provided.

In the capacitor of the present invention, the dielectric film is preferably composed of any one of an STO / BTO / STO and a BTO / STO / BTO stacked structure.

In addition, each of the STO thin film and the BTO thin film of the dielectric film is preferably formed of a plurality of STO unit layer and BTO unit layer, the lower electrode is poly-silicon (Poly-silicon), TiN, SrRuO ₃ , SiN, WN, It is preferable that any one of W, Pt, Co, Ni, YBCO, LSCO, CaRuO ₃ , (Ru, Sr) RuO ₃ , LaNiO ₃ , and in particular, the lower electrode is formed of polycrystalline silicon, It is preferable to be in direct contact.

In addition, according to the present invention to achieve the above object,

A lower electrode forming step of forming a lower electrode layer on the substrate, the lower electrode layer electrically connected to a transistor of the semiconductor memory device;

A dielectric film forming step of forming a dielectric film of a multi-layered structure by the STO thin film and the BTO thin film in atomic layer units on the lower electrode layer, wherein the dielectric film has a thickness at which phase transition due to naturally occurring strain occurs;

There is provided a capacitor manufacturing method of a semiconductor memory device comprising; forming an upper electrode on the dielectric film.

In the capacitor manufacturing method of the semiconductor memory device of the present invention,

The first type of forming the STO thin film in the dielectric film forming step is:

A) adsorbing said first raw material onto said substrate by contacting a gaseous first raw material comprising Sr on said substrate;

B) adding a purge gas to the substrate to remove excess of the first raw material and to form a first raw material layer having a thickness of monoatomic units;

C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti;

D) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the first raw material layer;

E) contacting the substrate with a gaseous oxide material to form an STO film by reacting the oxidized first raw material layer with a second raw material layer;

It is preferable to perform the steps a) to e) at least once in sequence.

The second type of forming the STO thin film in the dielectric film forming step is:

A) adsorbing said first raw material onto said substrate by contacting a gaseous first raw material comprising Sr on said substrate;

B) adding a purge gas to the substrate to remove excess of the first raw material and to form a first raw material layer having a thickness of monoatomic units;

C) oxidizing the first source material layer by contacting the substrate with a gaseous oxide;

D) applying a purge gas to the substrate to remove excess of the oxidized first raw material and to form an oxidized first raw material layer having a monoatomic unit thickness;

E) adsorbing the second raw material onto the oxidized first raw material layer by contacting the substrate with a gaseous second raw material containing Ti;

F) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the first raw material layer;

G) contacting the substrate with a gaseous oxide material to form an STO film by reacting the first raw material layer with the second raw material layer.

It is preferable to perform the steps a) to g) at least once in sequence.

The third type of forming the STO thin film in the dielectric film forming step is:

A) adsorbing said first raw material onto said substrate by contacting a gaseous first raw material comprising Sr on said substrate;

B) adding a purge gas to the substrate to remove excess of the first raw material and to form a first raw material layer having a thickness of monoatomic units;

C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti;

D) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the first raw material layer;

E) the first raw material oxidized by continuously contacting the substrate with a gaseous oxide material during the steps a) to d) so that the first and second raw material layers adsorbed on the substrate are oxidized. Forming an STO film from the layer and the second raw material layer;

It is preferable to perform the steps a) to e) at least once in sequence.

The first type of forming the BTO thin film in the dielectric film forming step is:

A) adsorbing said third raw material onto said substrate by contacting a gaseous third raw material comprising Ba on said substrate;

B) adding a purge gas to the substrate to remove excess of the third raw material and to form a third raw material layer having a thickness of monoatomic units;

C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti;

Applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the third raw material layer;

E) contacting the substrate with a gaseous oxide material to form a BTO film by reacting the third raw material layer with the second raw material layer;

It is preferable to perform the steps a) to e) at least once in sequence.

The second type of forming the BTO thin film in the dielectric film forming step is:

A) adsorbing said third raw material onto said substrate by contacting a gaseous third raw material comprising Ba on said substrate;

B) adding a purge gas to the substrate to remove excess of the third raw material and to form a third raw material layer having a thickness of monoatomic units;

C) oxidizing the third source material layer by contacting the substrate with a gaseous oxide;

D) adding a purge gas to the substrate to remove excess of the oxidized third raw material and to form an oxidized third raw material layer having a thickness of monoatomic units;

E) adsorbing a second raw material onto the oxidized third raw material layer by contacting the substrate with a gaseous second raw material containing Ti;

F) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the oxidized third raw material layer;

G) contacting the substrate with a gaseous oxide material to form a BTO film by reacting the oxidized third raw material layer with a second raw material layer;

It is preferable to perform the steps a) to g) at least once in sequence.

The third type of forming the BTO thin film in the dielectric film forming step is:

A) adsorbing said third raw material onto said substrate by contacting a gaseous third raw material comprising Ba on said substrate;

B) adding a purge gas to the substrate to remove excess of the third raw material and to form a third raw material layer having a thickness of monoatomic units;

C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti;

D) adding a purge gas to the substrate to remove excess of the second raw material, and forming a second raw material layer having a thickness of monoatomic units on the third raw material layer;

E) The third raw material material oxidized by continuously contacting the substrate with a gaseous oxide material during the steps a) to d) so that the third raw material layer and the second raw material layer adsorbed on the substrate are oxidized. Forming a BTO film from the layer and the second raw material layer;

It is preferable to perform the steps a) to e) at least once in sequence.

In the method of manufacturing a capacitor of a semiconductor memory device of the present invention, the first raw material is Sr (C ₅ ⁱ Pr ₃ H ₂ ) ₂ , SrS, Sr (thd) 2 (thd = 2, 2, 6, 6 -tetramethyl-3, 5-heptanedione), Sr (acac) ₂ , Sr (hfac) ₂ , Sr (tfac) ₂ , Sr (hfac) ₂ , Sr (TMFD) ₂ , [Sr (TMHD) ₂ ] L (L : lewis base), Sr (tmhd) ₂ (tetraglyme), Sr (tmhd) ₂ (pmdeta), [Sr (acac) ₂ ] L (L: lewis base), Sr (dpm) ₂ , Sr (metmhd) ₂ , It is preferred to include at least one selected from the group consisting of Sr (tmhd) ₂ (trine) _n .

The second raw material is Ti (O ⁱ Pr) ₄ , Ti (TMHD) ₂ (O ⁱ Pr) ₂ , Ti (acac) ₂ , Ti (thac) ₂ (O ⁱ Pr) ₂ , Ti (hfac ) ₂ (O ⁱ Pr) ₂ , Ti (TMHD) ₂ (O ⁿ Bu) ₂ , Ti (acac) ₂ (O ⁿ Bu) ₀ , Ti (tfac) ₂ (O ⁿ Bu) ₂ , Ti (hfac) ₂ (O ⁿ Bu) ₂ , Ti (TMHD) ₂ (NMe ₂ ) ₂ , Ti (TMHD) ₂ (dmae), Ti (Nme ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Ti (dmea) ₄ , Ti (dmea ) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ (nBuO) ₂ , Ti (tfac) ₂ (nBuO) ₂ , Ti (acac) ₂ (nBuO) ₂ , Ti (TMHD) 2 (nBuO) 2, Ti ( TMHD) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ ( ⁱ PrO) ₂ , Ti (tfac) ( ⁱ PrO) ₂ , Ti (acac) ₂ ( ⁱ PrO) ₂ , Ti (tmhd) ₂ (mpd) It is preferred to include at least one selected from the group consisting of.

In addition, the third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd ) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L It is preferable to include at least one selected from the group consisting of.

In the method of manufacturing a capacitor of a semiconductor memory device, the oxide may be H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H _4. It is preferable to include at least one selected from the group consisting of OH, nC ₄ H ₉ OH, the purge gas is preferably any one of argon (Ar) and nitrogen (N ₂ ).

In the process conditions of the capacitor manufacturing method of the semiconductor memory device, the temperature during the formation of the STO thin film and the BTO thin film in the step of forming the dielectric film is controlled within the range of 100 to 600 ℃, the thickness of the dielectric film is adjusted within the range of 50 to 500Å And it is preferable to form the STO thin film and the BTO thin film of the said dielectric film continuously in the same vacuum container.

Forming the dielectric film; Preferably, the dielectric film has a stacked structure of any one of STO / BTO / STO and BTO / STO / BTO, and at least one of the STO film and the BTO film is formed of a unit STO film or a BTO film.

In the method of manufacturing a capacitor of the present invention, the dielectric film is formed by continuously forming a thin film of STO and BTO by a digital chemical vapor deposition method in which a plurality of source gases are alternately injected into a same vacuum vessel, and the structural phase transition between the layers is reduced. By flowing, the dielectric constant is improved.

According to the capacitor of the present invention as described above and a method of manufacturing the same, a capacitor having a high dielectric constant can be obtained by using a phase shift caused by naturally occurring strain between dielectric films grown in a local epitaxial layer.

FIG. 2A shows the cubic BST structure of the paraelectric phase, and FIG. 2B shows the tetragonal BST structure of the ferroelectric phase.

The change in phase dielectric-strong dielectric properties is due to the ratio of Ba / Sr, and FIG. 3 shows a graph of lattice constant change according to the composition change of BaTiO ₃ -SrTiO ₃ system. That is, monotonic reduction from pure BTO (a = b = 3.994 kPa, c = 4.038 kPa) to pure STO (a = b = c = 3.905 kPa). It does not show the cubic structure.

The high dielectric properties are due to the vertical movement of the Ti atom centered on the cubic lattice. If the c-axis can be increased by compressing the a-axis and the b-axis as shown in FIG. The space that can increase the width of up and down can be increased to improve the dielectric characteristics, as shown by T.Kawakubo, K.Abe, S.Komatsu, K.Sano, N.Yanase and H.Mochizuki, IEEE 1996 gave. That is, if compressive stress is applied to the a- and b-axes of the BST lattice structure, the compressive stress is increased to the c-axis, and the dielectric constant of the dielectric film shown in the related art can be greatly improved by using a characteristic having a higher permittivity. .

The present invention continuously deposits STO and BTO to grow a local epitaxial thin film having a unique lattice constant of the STO and BTO so that a structural phase transition is induced.

According to the present invention, even when 30 mol (%) or more of STO is added, a BST thin film having a tetragonal structure can be obtained. This BST thin film is obtained by inducing strain due to the difference in lattice constant through successive deposition of STO and BTO in atomic layer units. In other words, in order for compressive stress to occur in the a-axis and b-axis of the BST structure, the STO is deposited on the substrate and then the BTO is deposited so that lattice mismatch occurs due to the lattice constant difference between the STO and the BTO.

4A and 4B are the first types of the STO thin film forming step and the BTO thin film forming step in the capacitor manufacturing method according to the present invention, and the order of raw material injection, purge gas injection, and oxide injection for the digital thin film deposition are shown. Shown flow chart shown.

The thin film formation process described below is performed in a vacuum vessel, in which a substrate is loaded, and the substrate is heated to a predetermined temperature. It is also assumed that a vacuum vessel is connected with an exhaust device for evacuating the interior, and a gas supply device for supplying various types of gases required is provided.

<< STO thin film formation >>

4A, 5A, and 6A, various types of STO thin film forming steps will be described.

Step 1 of forming the first type of STO thin film (see FIG. 4A)

A) First, a first raw material in a gaseous state, which is an Sr raw material, is injected into a vacuum container for a predetermined time so that the first raw material is adsorbed onto the surface of the substrate (11).

B) A purge gas is injected into the vacuum container so that the first raw material is adsorbed on the substrate in units of monoatomic layers, and the excess raw material is removed and exhausted by the purge gas (12).

C) The second raw material in a gaseous state, which is a Ti raw material, is injected into the vacuum container for a predetermined time to adsorb the second raw material onto the first raw material of the monoatomic layer (13).

D) Injecting the purge gas into the vacuum vessel, the second raw material is adsorbed on the first raw material (layer) in a unitary magnetic layer unit and the excess second raw material is removed and exhausted by the purge gas (14).

E) Injecting a gaseous oxide containing oxygen (O) into the vacuum container to form a unit STO thin film by mutual reaction between the first raw material and the second raw material (15).

F) A purge gas is injected into the vacuum vessel to remove and exhaust excess oxide material and reaction by-products (16).

By repeating the process of (a) to bar) (the process of reference numeral 11 to 16 in FIG. 4a) M times to form a desired thickness of the STO thin film in which the unit STO thin film is laminated in multiple. Here, the STO thin film may be composed of a unit STO thin film of one atomic layer unit or several layers of unit STO thin films according to the repetition number of times a) to bar).

Second type STO thin film forming step (see FIG. 5A)

A) First, a first raw material in a gaseous state, which is an Sr raw material, is injected into a vacuum container for a predetermined time so that the first raw material is adsorbed onto the surface of the substrate (11a).

B) A purge gas is injected into the vacuum container so that the first raw material is adsorbed on the substrate in units of monoatomic layers, and excess raw material is removed and exhausted by the purge gas (12a).

3) Oxidizing the first raw material by injecting a gaseous oxide containing oxygen (O) into the vacuum container (13a)

D) A purge gas is injected into the vacuum vessel to remove and exhaust excess oxide material and reaction by-products resulting from the oxidation reaction (14a).

E) The second raw material in a gaseous state, which is a Ti raw material, is injected into the vacuum container for a predetermined time to adsorb the second raw material onto the oxidized first raw material (15a).

F) A purge gas is injected into the vacuum container so that the second raw material is adsorbed on the oxidized first raw material in units of monoatomic layers and the excess second raw material is removed and exhausted (16a).

G) Injecting the oxide material into the vacuum vessel to form a unit STO thin film by the reaction between the first raw material and the second raw material (17a)

H) A purge gas is injected into the vacuum vessel to remove and exhaust excess oxide material and reaction by-products resulting from the oxidation reaction (18a).

The process of a) to a) (the process of reference numerals 11a to 18a in FIG. 5A) is repeated M times to form an STO thin film having a desired thickness in which unit STO thin films are stacked in multiple layers. Here, the STO thin film may be composed of one atomic layer unit STO thin film or several layers of unit STO thin films according to the repetition number of times a) to a).

Third type STO thin film forming step (see FIG. 6A)

A) First, the first raw material in the gaseous state, which is the Sr raw material and the oxide material, is injected into the vacuum container for a predetermined time so that the first raw material is oxidized on the surface of the substrate (11b and 15b).

B) The purge gas is injected into the vacuum vessel so that the first raw material oxide is adsorbed on the substrate in units of monoatomic layers, and excess raw material, oxide material and reaction by-products are removed and exhausted by the purge gas (12b, 15b). ).

C) The second raw material and the oxide material in the gaseous state, which are Ti raw materials, are injected into the vacuum vessel for a predetermined time and the second raw material is adsorbed on the oxidized first raw material in the oxidized state. Unit STO thin films in atomic layer units are formed of the two raw materials (13b and 15b).

D) A purge gas is injected into the vacuum vessel to remove and exhaust excess gas and reaction by-products other than the unit STO thin film (14b and 15b).

The steps A) to D) (processes of reference numerals 11b to 15b in FIG. 6A) are repeated M times to form an STO thin film having a desired thickness in which unit STO thin films are stacked in multiple layers. In this case, the STO thin film may be composed of one atomic layer unit STO thin film or several layers of unit STO thin films according to the repetition number of times a) to d). Here, the supply of oxide material may be supplied only at the time of supply of fuel material, or may be supplied continuously throughout the whole process.

<< BTO thin film formation >>

4B, 5B and 6B, various types of BTO thin film forming steps will be described.

Step of forming the first type of BTO thin film (see FIG. 4B)

A) A third raw material in a gaseous state, which is a Ba raw material, is first injected into a vacuum container in which the embedded substrate is heated to a predetermined temperature for a predetermined time to form the thin film formed by the above-described process on the surface of the substrate. And the third raw material is adsorbed onto the surface of the substrate (21).

B) A purge gas is injected into the vacuum vessel so that the third raw material is adsorbed on a substrate in unit monolayers and the excess raw material is removed and exhausted by the purge gas (22).

C) The second raw material in a gaseous state, which is a Ti raw material, is injected into the vacuum container for a predetermined time to adsorb the second raw material onto the first raw material of the monoatomic layer (23).

D) Injecting the purge gas into the vacuum vessel, the second raw material is adsorbed on the third raw material (layer) in units of monoatomic layer, and the excess second raw material is removed and exhausted by the purge gas (24).

E) Injecting a gaseous oxide containing oxygen (O) into the vacuum vessel to form a unit STO thin film by mutual reaction between the second raw material and the third raw material (25).

F) A purge gas is injected into the vacuum vessel to remove and exhaust excess oxide material and reaction by-products (26).

The process of a) to bar) (the process of reference numerals 11 to 16 in FIG. 4B) is repeated N times to form a BTO thin film having a desired thickness in which unit BTO thin films are stacked in multiple layers. Here, the BTO thin film may be composed of one atomic layer unit BTO thin film or several layers of unit BTO thin film according to the repetition number of times a) to bar).

The second type of BTO thin film forming step (see FIG. 5B)

A) First, a third raw material in a gaseous state, which is a Ba raw material, is injected into a vacuum container for a predetermined time so that the third raw material is adsorbed onto the surface of the substrate (21a).

B) A purge gas is injected into the vacuum container so that the third raw material is adsorbed on the substrate in unit monolayers and the excess raw material is removed and exhausted by the purge gas (22a).

3) The third raw material is oxidized by injecting a gaseous oxide containing oxygen (O) into the vacuum container (23a).

D) A purge gas is injected into the vacuum vessel to remove and exhaust excess oxide material and reaction by-products resulting from the oxidation reaction (24a).

E) the second raw material in a gaseous state, which is a Ti raw material, is injected into the vacuum container for a predetermined time to adsorb the second raw material onto the oxidized third raw material (25a).

F) A purge gas is injected into the vacuum container so that the second raw material is adsorbed on the oxidized third raw material in units of monoatomic layers, and the excess second raw material is removed and exhausted (26a).

G) Injecting the oxide material into the vacuum vessel to form a unit BTO thin film by the reaction between the third raw material and the second raw material (27a)

H) A purge gas is injected into the vacuum vessel to remove and exhaust excess oxide material and reaction by-products resulting from the oxidation reaction (28a).

The process of a) to a) (the process of reference numerals 21a to 28a in FIG. 5B) is repeated N times to form a BTO thin film having a desired thickness in which unit BTO thin films are stacked in multiple layers. Here, the BTO thin film may be composed of one atomic layer unit BTO thin film or several layers of unit BTO thin film according to the repetition number of times a) to h).

Third type BTO thin film forming step (see FIG. 6B)

A) First, a third raw material of a gaseous state, which is a Ba raw material, and an oxide material is injected into a vacuum container for a predetermined time so that the third raw material is adsorbed to the surface of the substrate in an oxidized state (21b, 25b).

B) Injecting the purge gas into the vacuum vessel, allowing the third raw material oxide to be adsorbed on the substrate in units of monoatomic layers, and removing the excess raw material, oxide material and reaction by-products by purge gas (22b, 25b). ).

C) The second raw material and the oxide material in the gaseous state, which are Ti raw materials, are injected into the vacuum vessel for a predetermined time and the second raw material is adsorbed on the oxidized third raw material in the oxidized state, thereby allowing the third raw material and the Unit BTO thin films in atomic layer units are formed of binary raw materials (23b and 25b).

D) A purge gas is injected into the vacuum vessel to remove and exhaust excess gas and reaction by-products other than the unit BTO thin film (24b and 25b).

The process of a) to d) (refer to reference numerals 21b to 25b in FIG. 6b) is repeated N times to form a BTO thin film having a desired thickness in which unit BTO thin films are stacked in multiple layers. Here, the BTO thin film may be composed of one atomic layer unit BTO thin film or several layers of unit BTO thin film according to the repetition number of times a) to d). Here, the supply of oxide material may be supplied only at the time of supply of fuel material, or may be supplied continuously throughout the whole process.

As described above, the method for forming a thin film according to the present invention, unlike the conventional chemical vapor deposition method, reacts the material of the thin film to be deposited by flowing into the reaction tubes at predetermined time intervals, respectively. That is, during one cycle for forming one unit STO thin film and a BTO thin film, gaseous raw materials are alternately injected into a vacuum container equipped with a substrate for a semiconductor memory device. At this time, vacuum evacuation is continued as in a conventional deposition apparatus, and the substrate is heated to a predetermined temperature. At this time, in the manufacturing method of this invention, the temperature of a board | substrate is maintained about 100-600 degreeC.

As a raw material for the deposition of STO, Sr uses Sr (C ₅ -i-Pr ₃ H ₂ ), Ti is Ti (O ⁱ Pr) ₄ , and water (H ₂ O) is used as a raw material of the oxide. It is preferable to use nitrogen (N ₂ ) as the gas for transporting the reactants. Sr (C ₅ ⁱ Pr ₃ H ₂ ) ₂ , SrS, Sr (thd) 2 (thd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione) , Sr (acac) ₂ , Sr (hfac) ₂ , Sr (tfac) ₂ , Sr (hfac) ₂ , Sr (TMFD) ₂ , [Sr (TMHD) ₂ ] L (L: lewis base), Sr (tmhd) ₂ (tetraglyme), Sr (tmhd) ₂ (pmdeta), [Sr (acac) ₂ ] L (L: lewis base), Sr (dpm) ₂ , Sr (metmhd) ₂ , Sr (tmhd) ₂ (trine) _n At least one of them can be applied.

In addition, as a second source material that can be used as a Ti source, Ti (O ⁱ Pr) ₄ , Ti (TMHD) ₂ (O ⁱ Pr) ₂ , Ti (acac) ₂ , Ti (thac) ₂ (O ⁱ Pr) ₂ , Ti (hfac) ₂ (O ⁱ Pr) ₂ , Ti (TMHD) ₂ (O ⁿ Bu) ₂ , Ti (acac) ₂ (O ⁿ Bu) ₀ , Ti (tfac) ₂ (O ⁿ Bu) ₂ , Ti (hfac) ₂ (O ⁿ Bu) ₂ , Ti (TMHD) ₂ (NMe ₂ ) ₂ , Ti (TMHD) ₂ (dmae), Ti (Nme ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Ti (dmea) ₄ , Ti (dmea) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ (nBuO) ₂ , Ti (tfac) ₂ (nBuO) ₂ , Ti (acac) ₂ (nBuO) ₂ , Ti (TMHD) 2 (nBuO 2, Ti (TMHD) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ ( ⁱ PrO) ₂ , Ti (tfac) ₂ ( ⁱ PrO) ₂ , Ti (acac) ₂ ( ⁱ PrO) ₂ , Ti (tmhd) At least one of ₂ (mpd) may be applied.

As the oxide, any one of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH and nC ₄ H ₉ OH can be selected. Can be.

STO is deposited on the substrate by reaction kinetics as in Scheme 1 below.

Sr (C ₅ -i-Pr ₃ H ₂ ) + Ti (O ⁱ Pr) ₄ + H ₂ O ----------> SrTiO ₃ + by-product

In order to induce the reaction as described above, for example, first, a gaseous Sr raw material is supplied to a vacuum vessel equipped with a substrate for a predetermined time. In this way, a layer of Sr raw material is accumulated on the substrate. Subsequently, when the purge gas is injected, the surplus Sr raw material accumulated in two layers on the substrate is discharged to the outside of the vacuum container due to the pressure of the purge gas, and the Sr raw material layer in atomic layer units remains on the substrate.

Subsequently, the gaseous Ti raw material is injected into the vacuum container for a predetermined time. In this way, the Ti raw material is also adsorbed atomically on the substrate. A layer of Ti raw material is deposited on the substrate. Subsequently, when the purge gas is injected, the excess Ti raw material is discharged to the outside of the vacuum vessel by the pressure of the purge gas, and the Ti raw material layer in atomic layer units remains on the substrate.

Finally, when gaseous oxide is injected into the vacuum vessel, the reaction is performed by the same mechanism as in Scheme 1, thereby forming an STO film on the substrate.

After the STO film is formed, the purge gas is again injected into the vacuum vessel, and the surplus and by-products on the substrate and the substrate are discharged to the outside of the vacuum vessel.

In the above process, the purge gas removes the surplus raw material so that only a single layer of raw material remains on the substrate and prevents the surplus material from reacting with other raw materials. As a result, the atomic layer unit The STO film of this can be obtained.

Ba (C ₅ Me ₅ ) ₂ , Ba is Ti (O ⁱ Pr) ₄ , Ba is used as a raw material for the deposition of BTO, and water (H ₂ O) is used as the raw material of the oxide. Nitrogen (N ₂ ) is preferably used as the gas for this purpose.

Third raw materials that can be used as a Ba source are Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) -C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba ( acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac ) ₂ can be applied to at least any one of L.

A detailed mechanism of the BTO reaction is shown below in the form of BTO on the substrate with the following reaction kinetics.

Ba (C ₅ Me ₅ ) ₂ + Ti (O ⁱ Pr) ₄ + H ₂ O ----------> BaTiO ₃ + by-product

When the Ba raw material in the gas state is brought into contact with the substrate on which the STO film is formed, the Ba raw material layer in the atomic layer unit is adsorbed on the substrate, and then a vacuum container including the raw material stacked on the substrate by two or more layers is purged. Surplus raw material in the product is discharged.

When the Ti raw material is injected in the same manner and then the purge gas is supplied, the Ti raw material layer in atomic layer units is formed on the substrate. Subsequently, when the oxide material is injected into the vacuum vessel, the reaction is performed as in Scheme 2, thereby forming a BTO film on the STO film. When the purge gas is injected for a predetermined time, after the formation of the BTO film, the remaining surplus substance and the remaining substance are discharged to the outside of the vacuum vessel.

When the above-described process of forming the STO film and the BTO film is repeated once to several times, the BST of the high dielectric constant desired in the present invention is formed in atomic layer units.

According to the present invention, after depositing one atomic layer of STO by Equation (1) above, depositing one atomic layer of BTO by Equation (2) and then repeating this to form a composite layer or (2) It is preferable to deposit one atomic layer of STO by (1) after atomic layer deposition, and to deposit a certain thickness by repeating this.

According to the present invention, it is preferable to deposit STO to a critical thickness by Equation (1), and then deposit BTO to a critical thickness by Equation (2), and then deposit STO by Equation (1).

According to the present invention, by depositing the STO film to the critical thickness by the above scheme 1, and then depositing the BTO film to the critical thickness by the scheme 2, and again by depositing the STO film by the threshold thickness by the scheme 1, STO / BTO / A dielectric film of an STO laminated structure can be obtained.

Preferred lamination structures obtained by the above method are STO / BTO / STO, BTO / STO / BTO, and at least one of the STO film and the BTO film is preferably formed so as to be made of a unit STO film or a BTO film. .

FIG. 7A is a flow chart showing a method of manufacturing a capacitor of a semiconductor memory according to the present invention for forming a BST dielectric film having an STO / BTO / STO stacked structure, and the present invention for forming a BST dielectric film having a BTO / STO / BTO stacked structure. A flowchart showing a method of manufacturing a capacitor of a semiconductor memory according to the present invention.

First, referring to FIG. 7A, in order to form a BST dielectric film having an STO / BTO / STO stacked structure, an STO thin film forming step 31 is first performed, followed by a BTO thin film forming step 32, and then an STO. The thin film forming step 33 is performed.

In addition, referring to FIG. 7B, in order to form a BST dielectric film having a BTO / STO / BTO stacked structure, a BTO thin film forming step 41 is first performed, followed by an STO thin film forming step 42, followed by STO. The thin film forming step 43 is performed.

The process illustrated in FIGS. 7A and 7B may be performed only once each, or may be repeated X and Y times respectively, and each STO and BTO thin film forming step is a step of the type shown in FIGS. 5 to 7. Can be adopted. According to the present invention, a BST dielectric film having various laminated structures can be obtained. For example, according to the present invention, the BST dielectric film may be STO / BTO / STO, BTO / STO / BTO, BTO / BTO / STO / BTO, STO / BTO / BTO / STO stacked structure, or these stacked structures repeatedly stacked in multiple layers. It can have a structure.

8 shows a schematic cross-sectional view of a first embodiment of a semiconductor memory device according to the present invention.

Referring to FIG. 8, a stacked structure constituting a transistor is disposed on a lower layer on a substrate 10, and a capacitor according to the present invention is disposed on the stacked structure. The capacitor has a dielectric film having an STO / BTO / STO stacked structure, and upper and lower electrodes are positioned above and below it. The function of the lower electrode is a polysilicon layer electrically connected to the drain of the transistor.

9 shows a schematic cross-sectional view of a second embodiment of a semiconductor memory device according to the present invention.

Referring to FIG. 9, a stacked structure constituting a transistor is disposed on a lower layer on a substrate, and a capacitor according to the present invention is positioned on the stacked structure. The capacitor has a BST dielectric film having an STO / STO / BTO / STO stacked structure, and upper and lower electrodes are positioned above and below it. The function of the lower electrode is a polysilicon layer electrically connected to the drain of the transistor.

As described above, the dielectric film of the STO / BTO / STO laminated structure and the BTO / STO / BTO laminated structure includes BTO / STO / BTO, STO / STO / BTO, BTO / STO / STO, STO / STO / BTO / STO / STO It is possible to change to various types of structures such as /BTO../STO and BTO / STO / STO ../ BTO laminated structure. However, in the case of any laminated structure, the overall thickness of the dielectric film is preferably adjusted within the range of 50 to 500 GPa.

The lower electrode may be formed of TiN, SrRuO ₃ , SiN, WN, W, Pt, Co, Ni, YBCO, LSCO, CaRuO ₃ , (Ru, Sr) RuO ₃ , LaNiO _3, or the like as described above. This can be applied. In particular, when the polysilicon is a lower electrode, the lower electrode does not have a diffusion barrier as in the prior art and is in direct contact with the dielectric film. This is possible because the capacitor and the manufacturing method of the present invention form the dielectric film in a low temperature state rather than a high temperature.

According to the present invention, by continuously depositing STO and BTO, not only can control the atomic layer thickness and obtain a uniform thin film, but also can induce lattice deformation, thereby obtaining a dielectric film having a high dielectric constant.

In addition, by depositing the STO and BTO continuously, it can be controlled by the cycle of sending the reactant by using the principle of depositing the capacitor dielectric film thickness thinner in the high-integration device one atomic layer per cycle.

Although the present invention has been described with reference to the embodiments shown in the drawings, this is merely illustrative, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention should be defined only in the appended claims.

Claims (79)

A capacitor of a semiconductor memory device comprising a dielectric film and upper and lower electrodes positioned above and below the dielectric film. The dielectric film is composed of a multi-layered structure consisting of STO thin film and BTO thin film of alternating atomic layer unit thickness, and the dielectric film has a thickness in which phase transition due to naturally occurring strain is generated. Capacitor of the device. The method of claim 1, The dielectric film has a stacked structure of any one of STO / BTO / STO, BTO / STO / BTO capacitor of the semiconductor memory device. The method of claim 2, And the dielectric film has a stacked structure in which STO / BTO / STO and BTO / STO / BTO stacked structures are stacked in multiple layers. The method according to any one of claims 1 to 3, And the STO thin film and the BTO thin film of the dielectric film are each formed of a plurality of unit STO thin films and BTO thin films. The method of claim 1, wherein The lower electrode is any one of poly-silicon, TiN, SrRuO ₃ , SiN, WN, W, Pt, Co, Ni, YBCO, LSCO, CaRuO ₃ , (Ru, Sr) RuO ₃ , LaNiO ₃ A capacitor of a semiconductor memory device, characterized in that. The method of claim 4, wherein The lower electrode is any one of poly-silicon, TiN, SrRuO ₃ , SiN, WN, W, Pt, Co, Ni, YBCO, LSCO, CaRuO ₃ , (Ru, Sr) RuO ₃ , LaNiO ₃ A capacitor of a semiconductor memory device, characterized in that. The method of claim 5, And the lower electrode is made of polycrystalline silicon and is in direct contact with the dielectric film. The method of claim 6, And the lower electrode is made of polycrystalline silicon and is in direct contact with the dielectric film. A lower electrode forming step of forming a lower electrode layer on the substrate, the lower electrode layer electrically connected to a transistor of the semiconductor memory device; A dielectric film forming step of forming a dielectric film of a multi-layered structure by the STO thin film and the BTO thin film in atomic layer units on the lower electrode layer, wherein the dielectric film has a thickness at which phase transition due to naturally occurring strain occurs; And an upper electrode forming step of forming an upper electrode on the dielectric layer. The method of claim 9, Forming the STO thin film in the dielectric film forming step: A) adsorbing said first raw material onto said substrate by contacting a gaseous first raw material comprising Sr on said substrate; B) adding a purge gas to the substrate to remove excess of the first raw material and to form a first raw material layer having a thickness of monoatomic units; C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti; D) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the first raw material layer; E) contacting the substrate with a gaseous oxide material to form an STO film by reacting the oxidized first raw material layer with a second raw material layer; The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the steps a) to e) are performed at least once. The method of claim 9, Forming the STO thin film in the dielectric film forming step: A) adsorbing said first raw material onto said substrate by contacting a gaseous first raw material comprising Sr on said substrate; B) adding a purge gas to the substrate to remove excess of the first raw material and to form a first raw material layer having a thickness of monoatomic units; C) oxidizing the first source material layer by contacting the substrate with a gaseous oxide; D) applying a purge gas to the substrate to remove excess of the oxidized first raw material and to form an oxidized first raw material layer having a monoatomic unit thickness; E) adsorbing the second raw material onto the oxidized first raw material layer by contacting the substrate with a gaseous second raw material containing Ti; F) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the first raw material layer; G) contacting the substrate with a gaseous oxide material to form an STO film by reacting the first raw material layer with the second raw material layer. The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the steps a) to g) are sequentially performed at least once. The method of claim 9, Forming the STO thin film in the dielectric film forming step: A) adsorbing said first raw material onto said substrate by contacting a gaseous first raw material comprising Sr on said substrate; B) adding a purge gas to the substrate to remove excess of the first raw material and to form a first raw material layer having a thickness of monoatomic units; C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti; D) adding a purge gas to the substrate to remove excess of the second raw material, and forming a second raw material layer having a thickness of monoatomic units on the first raw material layer; E) the first raw material oxidized by continuously contacting the substrate with a gaseous oxide material during the steps a) to d) so that the first and second raw material layers adsorbed on the substrate are oxidized. Forming an STO film from the layer and the second raw material layer; The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the steps a) to e) are performed at least once. The method according to any one of claims 9 to 12, Forming the BTO thin film in the dielectric film forming step is: A) adsorbing said third raw material onto said substrate by contacting a gaseous third raw material comprising Ba on said substrate; B) adding a purge gas to the substrate to remove excess of the third raw material and to form a third raw material layer having a thickness of monoatomic units; C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti; Applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the third raw material layer; E) contacting the substrate with a gaseous oxide material to form a BTO film by reacting the third raw material layer with the second raw material layer; The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the steps a) to e) are performed at least once. The method according to any one of claims 9 to 12, Forming the BTO thin film in the dielectric film forming step is: A) adsorbing said third raw material onto said substrate by contacting a gaseous third raw material comprising Ba on said substrate; B) adding a purge gas to the substrate to remove excess of the third raw material and to form a third raw material layer having a thickness of monoatomic units; C) oxidizing the third source material layer by contacting the substrate with a gaseous oxide; D) adding a purge gas to the substrate to remove excess of the oxidized third raw material and to form an oxidized third raw material layer having a thickness of monoatomic units; E) adsorbing a second raw material onto the oxidized third raw material layer by contacting the substrate with a gaseous second raw material containing Ti; F) applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the oxidized third raw material layer; G) contacting the substrate with a gaseous oxide material to form a BTO film by reacting the oxidized third raw material layer with a second raw material layer; The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the steps a) to g) are sequentially performed at least once. The method according to any one of claims 9 to 12, Forming the BTO thin film in the dielectric film forming step is: A) adsorbing said third raw material onto said substrate by contacting a gaseous third raw material comprising Ba on said substrate; B) adding a purge gas to the substrate to remove excess of the third raw material and to form a third raw material layer having a thickness of monoatomic units; C) adsorbing a second raw material onto the first raw material layer by contacting the substrate with a gaseous second raw material containing Ti; Applying a purge gas to the substrate to remove excess of the second raw material and to form a second raw material layer having a thickness of monoatomic units on the third raw material layer; E) The third raw material material oxidized by continuously contacting the substrate with a gaseous oxide material during the steps a) to d) so that the third raw material layer and the second raw material layer adsorbed on the substrate are oxidized. Forming a BTO film from the layer and the second raw material layer; The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the steps a) to e) are performed at least once. The method according to any one of claims 10 to 12, The first raw material is Sr (C ₅ ⁱ Pr ₃ H ₂ ) ₂ , SrS, Sr (thd) 2 (thd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Sr (acac) ₂ , Sr (hfac) ₂ , Sr (tfac) ₂ , Sr (hfac) ₂ , Sr (TMFD) ₂ , [Sr (TMHD) ₂ ] L (L: lewis base), Sr (tmhd) ₂ (tetraglyme), In the group consisting of Sr (tmhd) ₂ (pmdeta), [Sr (acac) ₂ ] L (L: lewis base), Sr (dpm) ₂ , Sr (metmhd) ₂ , Sr (tmhd) ₂ (trine) _n Capacitor manufacturing method of a semiconductor memory device comprising at least one selected. The method of claim 13, The first raw material is Sr (C ₅ ⁱ Pr ₃ H ₂ ) ₂ , SrS, Sr (thd) 2 (thd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Sr (acac) ₂ , Sr (hfac) ₂ , Sr (tfac) ₂ , Sr (hfac) ₂ , Sr (TMFD) ₂ , [Sr (TMHD) ₂ ] L (L: lewis base), Sr (tmhd) ₂ (tetraglyme), In the group consisting of Sr (tmhd) ₂ (pmdeta), [Sr (acac) ₂ ] L (L: lewis base), Sr (dpm) ₂ , Sr (metmhd) ₂ , Sr (tmhd) ₂ (trine) _n Capacitor manufacturing method of a semiconductor memory device comprising at least one selected. The method of claim 14, The first raw material is Sr (C ₅ ⁱ Pr ₃ H ₂ ) ₂ , SrS, Sr (thd) 2 (thd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Sr (acac) ₂ , Sr (hfac) ₂ , Sr (tfac) ₂ , Sr (hfac) ₂ , Sr (TMFD) ₂ , [Sr (TMHD) ₂ ] L (L: lewis base), Sr (tmhd) ₂ (tetraglyme), In the group consisting of Sr (tmhd) ₂ (pmdeta), [Sr (acac) ₂ ] L (L: lewis base), Sr (dpm) ₂ , Sr (metmhd) ₂ , Sr (tmhd) ₂ (trine) _n Capacitor manufacturing method of a semiconductor memory device comprising at least one selected. The method of claim 15, The first raw material is Sr (C ₅ ⁱ Pr ₃ H ₂ ) ₂ , SrS, Sr (thd) 2 (thd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Sr (acac) ₂ , Sr (hfac) ₂ , Sr (tfac) ₂ , Sr (hfac) ₂ , Sr (TMFD) ₂ , [Sr (TMHD) ₂ ] L (L: lewis base), Sr (tmhd) ₂ (tetraglyme), In the group consisting of Sr (tmhd) ₂ (pmdeta), [Sr (acac) ₂ ] L (L: lewis base), Sr (dpm) ₂ , Sr (metmhd) ₂ , Sr (tmhd) ₂ (trine) _n Capacitor manufacturing method of a semiconductor memory device comprising at least one selected. The method according to any one of claims 10 to 12 and 17 to 19, The second raw material is Ti (O ⁱ Pr) ₄ , Ti (TMHD) ₂ (O ⁱ Pr) ₂ , Ti (acac) ₂ , Ti (thac) ₂ (O ⁱ Pr) ₂ , Ti (hfac) ₂ (O ⁱ Pr) ₂ , Ti (TMHD) ₂ (O ⁿ Bu) ₂ , Ti (acac) ₂ (O ⁿ Bu) ₀ , Ti (tfac) ₂ (O ⁿ Bu) ₂ , Ti (hfac) ₂ (O ⁿ Bu) ₂ , Ti (TMHD) ₂ (NMe ₂ ) ₂ , Ti (TMHD) ₂ (dmae), Ti (Nme ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Ti (dmea) ₄ , Ti (dmea) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ (nBuO) ₂ , Ti (tfac) ₂ (nBuO) ₂ , Ti (acac) ₂ (nBuO) ₂ , Ti (TMHD) 2 (nBuO) 2, Ti (TMHD) _Group consisting of ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ ( ⁱ PrO) ₂ , Ti (tfac) ( ⁱ PrO) ₂ , Ti (acac) ₂ ( ⁱ PrO) ₂ , Ti (tmhd) ₂ (mpd) Capacitor manufacturing method of a semiconductor memory device comprising at least one selected from. The method of claim 13, The second raw material is Ti (O ⁱ Pr) ₄ , Ti (TMHD) ₂ (O ⁱ Pr) ₂ , Ti (acac) ₂ , Ti (thac) ₂ (O ⁱ Pr) ₂ , Ti (hfac) ₂ (O ⁱ Pr) ₂ , Ti (TMHD) ₂ (O ⁿ Bu) ₂ , Ti (acac) ₂ (O ⁿ Bu) ₀ , Ti (tfac) ₂ (O ⁿ Bu) ₂ , Ti (hfac) ₂ (O ⁿ Bu) ₂ , Ti (TMHD) ₂ (NMe ₂ ) ₂ , Ti (TMHD) ₂ (dmae), Ti (Nme ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Ti (dmea) ₄ , Ti (dmea) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ (nBuO) ₂ , Ti (tfac) ₂ (nBuO) ₂ , Ti (acac) ₂ (nBuO) ₂ , Ti (TMHD) 2 (nBuO) 2, Ti (TMHD) _Group consisting of ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ ( ⁱ PrO) ₂ , Ti (tfac) ( ⁱ PrO) ₂ , Ti (acac) ₂ ( ⁱ PrO) ₂ , Ti (tmhd) ₂ (mpd) Capacitor manufacturing method of a semiconductor memory device comprising at least one selected from. The method of claim 14, The second raw material is Ti (O ⁱ Pr) ₄ , Ti (TMHD) ₂ (O ⁱ Pr) ₂ , Ti (acac) ₂ , Ti (thac) ₂ (O ⁱ Pr) ₂ , Ti (hfac) ₂ (O ⁱ Pr) ₂ , Ti (TMHD) ₂ (O ⁿ Bu) ₂ , Ti (acac) ₂ (O ⁿ Bu) ₀ , Ti (tfac) ₂ (O ⁿ Bu) ₂ , Ti (hfac) ₂ (O ⁿ Bu) ₂ , Ti (TMHD) ₂ (NMe ₂ ) ₂ , Ti (TMHD) ₂ (dmae), Ti (Nme ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Ti (dmea) ₄ , Ti (dmea) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ (nBuO) ₂ , Ti (tfac) ₂ (nBuO) ₂ , Ti (acac) ₂ (nBuO) ₂ , Ti (TMHD) 2 (nBuO) 2, Ti (TMHD) _Group consisting of ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ ( ⁱ PrO) ₂ , Ti (tfac) ( ⁱ PrO) ₂ , Ti (acac) ₂ ( ⁱ PrO) ₂ , Ti (tmhd) ₂ (mpd) Capacitor manufacturing method of a semiconductor memory device comprising at least one selected from. The method of claim 15, The second raw material is Ti (O ⁱ Pr) ₄ , Ti (TMHD) ₂ (O ⁱ Pr) ₂ , Ti (acac) ₂ , Ti (thac) ₂ (O ⁱ Pr) ₂ , Ti (hfac) ₂ (O ⁱ Pr) ₂ , Ti (TMHD) ₂ (O ⁿ Bu) ₂ , Ti (acac) ₂ (O ⁿ Bu) ₀ , Ti (tfac) ₂ (O ⁿ Bu) ₂ , Ti (hfac) ₂ (O ⁿ Bu) ₂ , Ti (TMHD) ₂ (NMe ₂ ) ₂ , Ti (TMHD) ₂ (dmae), Ti (Nme ₂ ) ₄ , Ti (NEt ₂ ) ₄ , Ti (dmea) ₄ , Ti (dmea) ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ (nBuO) ₂ , Ti (tfac) ₂ (nBuO) ₂ , Ti (acac) ₂ (nBuO) ₂ , Ti (TMHD) 2 (nBuO) 2, Ti (TMHD) _Group consisting of ₂ ( ⁱ PrO) ₂ , Ti (hfac) ₂ ( ⁱ PrO) ₂ , Ti (tfac) ( ⁱ PrO) ₂ , Ti (acac) ₂ ( ⁱ PrO) ₂ , Ti (tmhd) ₂ (mpd) Capacitor manufacturing method of a semiconductor memory device, characterized in that it comprises at least one selected from. The method according to any one of claims 10 to 12, 17 to 19 and 21 to 23, The third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L Capacitor manufacturing method of a semiconductor memory device characterized in that it comprises at least one selected from the group. The method of claim 13, The third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L Capacitor manufacturing method of a semiconductor memory device characterized in that it comprises at least one selected from the group. The method of claim 14, The third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L Capacitor manufacturing method of a semiconductor memory device characterized in that it comprises at least one selected from the group. The method of claim 15, The third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L Capacitor manufacturing method of a semiconductor memory device characterized in that it comprises at least one selected from the group. The method of claim 16, The third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L Capacitor manufacturing method of a semiconductor memory device characterized in that it comprises at least one selected from the group. The method of claim 20, The third raw material is Ba (DPM) ₂ , Ba (O ₂ C ₂ H (C ₂ H ₅ ) —C ₄ H ₉ ) ₂ , Ba (C ₅ Me ₅ ) ₂ , Ba (acac) ₂ , Ba (tfac) ₂ , Ba (hfac) ₂ , Ba (tmhd) ₂ (tmhd = 2, 2, 6, 6-tetramethyl-3, 5-heptanedione), Ba (TMHD) ₂ (tetraglyme), Ba (tmhd) ₂ (pmdeta), Ba (tmhd) ₂ (tetraen), Ba (metmhd) ₂ , Ba (tmhd) ₂ (trine) _n , Ba (TMHD) ₂ L (L: lewis base), Ba (acac) ₂ L Capacitor manufacturing method of a semiconductor memory device characterized in that it comprises at least one selected from the group. The method according to any one of claims 10 to 12, 17 to 19, 21 to 23 and 25 to 29, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method of claim 13, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method of claim 14, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method of claim 15, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method of claim 16, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method of claim 20, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method of claim 24, The oxide material is in the group consisting of H ₂ O, O ₂ , O ₃ , N ₂ O, H ₂ O ₂ , CH ₃ OH, CH ₂ OHC ₂ OH, tC ₂ H ₄ OH, nC ₄ H ₉ OH A method for manufacturing a semiconductor memo device, characterized in that it comprises at least one selected. The method according to any one of claims 10 to 12, 17 to 19, 21 to 23, 25 to 29 and 31 to 36, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 13, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 14, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 15, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 16, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 20, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 24, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. The method of claim 30, The purge gas is argon (Ar) and nitrogen (N ₂ ) of any one of the capacitor manufacturing method of the semiconductor memory device, characterized in that. Claims 10 to 12, 17 to 19, 21 to 23, 25 to 29, 31 to 36 and 38 to 44 In The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 13, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 14, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 15, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 16, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 20, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 24, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 30, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. The method of claim 37, The method of manufacturing a capacitor of a semiconductor memory device, characterized in that the temperature is controlled within the range of 100 to 600 ℃ when forming the STO thin film and the BTO thin film in the dielectric film forming step. Claims 10 to 12, 17 to 19, 21 to 23, 25 to 29, 31 to 36, 38 to 44 and 46 to 46 The compound of any one of claims 53, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 13, And controlling the thickness of the dielectric film within the range of 50 to 500 kV. The method of claim 14, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 15, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 16, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 20, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 24, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 30, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 37, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. The method of claim 45, A method of manufacturing a capacitor of a semiconductor memory device, characterized in that the thickness of the dielectric film is adjusted within the range of 50 to 500 kV. Claims 10 to 12, 17 to 19, 21 to 23, 25 to 29, 31 to 36, 38 to 44, 46 to 46 64. The compound of any of claims 53 and 55-63, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 13, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 14, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 15, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 16, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 20, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 24, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 30, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 37, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 45, And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. The method of claim 64, wherein And the STO thin film and the BTO thin film of the dielectric film are successively formed in the same vacuum container. Claims 9 to 12, 17 to 19, 21 to 23, 25 to 29, 31 to 36, 38 to 44 and 46 to 78. The method of any of claims 53, 55-63 and 65-74, The dielectric film forming step may include: forming an STO film and a BTO film such that the dielectric film has a stacked structure of any one of STO / BTO / STO and BTO / STO / BTO. 76. The method of claim 75 wherein The dielectric film forming step may include: stacking one of the STO / BTO / STO and BTO / STO / BTO stacked structures in which the dielectric film has a stacked structure in which multiple layers are repeatedly stacked. Capacitor. 76. The method of claim 75 wherein The dielectric film forming step may include: forming at least one of an STO thin film and a BTO thin film of the dielectric film to include a plurality of unit STO thin films or a BTO thin film. 77. The method of claim 76, The dielectric film forming step may include: forming at least one of an STO thin film and a BTO thin film of the dielectric film to include a plurality of unit STO thin films or a BTO thin film. Claims 9 to 12, 17 to 19, 21 to 23, 25 to 29, 31 to 36, 38 to 44 and 46 to 78. The method of any of claims 53, 55-63 and 65-74, The dielectric film forming step may include: forming at least one of the STO thin film and the BTO thin film of the dielectric film to include a plurality of unit STO thin films or BTO thin films.