KR20220155922A - Bottom up thin film composition, method for forming thin film and semiconductor device prepared therefrom - Google Patents

Abstract

The present invention relates to a bottom up thin film composition, a method for forming a thin film using the same, and a semiconductor device manufactured therefrom. According to the present invention, even when a thin film is formed on a substrate having a complex structure by lowering a growth rate, a conformal thin film is provided in a bottom up method. By reducing impurities in the thin film and greatly improving the density of the thin film, a leakage current caused by oxidation of a lower electrode in a conventional high-temperature process is greatly reduced. The bottom up thin film composition comprises a pulse precursor.

Description

Bottom-up thin film composition, thin film formation method using the same, and semiconductor device manufactured therefrom

The present invention relates to a bottom-up thin film composition, a method for forming a thin film using the same, and a semiconductor device manufactured therefrom, and more particularly, to an inorganic precursor included in the bottom-up thin film composition as a pulse precursor remaining in the thin film and a non-remaining inorganic precursor in the thin film. Including organic precursors to control the thin film formation rate and at the same time to manufacture high-purity thin films, manufacture conformal and dense thin films by bottom-up method, and improve the film quality formed through chemical reaction with the substrate to achieve crystallinity and to reduce leakage current by reducing the impurity concentration in the thin film, and relates to a thin film forming method using the same and a semiconductor substrate manufactured therefrom.

Recently, in the field of semiconductor technology, research on suitable materials and process technologies is being actively conducted by pursuing more advanced technologies through miniaturization of semiconductor devices. In particular, the process of manufacturing oxide thin films such as TiO ₂ , ZrO ₂ , HfO ₂ , Al ₂ O ₃ , which are high-k materials used in capacitors for DRAM (Dynamic Random Access Memory) among semiconductor processes, has been extensively researched. It is becoming.

In semiconductor manufacturing, metal oxide thin film manufacturing processes such as metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) are widely used, and there are various limitations when forming metal oxide thin films through chemical vapor deposition and atomic layer deposition. First of all, the miniaturization of the semiconductor device and the generation of leakage current due to the oxidation of the lower electrode due to the high-temperature process, and the low crystallinity of the thin film at a limited temperature show the limit of capacitance.

Capacitors for DRAM require high capacitance and a leakage current of 10 ^-7 A/cm ² or less. In particular, leakage current is a major variable in meeting the ever-decreasing stringent requirements of DRAM cells and providing a thin dielectric film. ( W.Jeon, Journal of Materials Research 35(7), 1 (2019) and J.Lee, D.Park, S.Yew, S. Shin, J. Noh, H. Kim, B. Choi, IEEE Electron Device Letters 38 (11) (2017) ).

Niinisto et al. post-annealed an amorphous thin film and a monoclinic thin film with a thickness of 8.6 nm at 500 °C through ALD of HfO ₂ at 250 to 400 °C using CpHf(NMe ₂ ) ₃ and ozone. , reported a leakage current intensity of 1 x 10 ^-7 A/cm ² at 1 V ( J. Niinisto, M. Mantymaki, K. Kukli, L. Costelle, E. Puukilainen, M. Ritala, M. Leskela, Journal of Crystal Growth, 312, 245 (2010) ).

However, it is known that bulk-related leakage conduction mechanisms such as trap-assisted tunneling (TAT) or Poole-Frenkel (PF) emission dominate instead of interface-related leakage current conduction in ZrO ₂ and HfO ₂ ( WY Choi, G.Yoon , WYChung, Y.Cho, S. SHin and KHAhn, Micromachines 10, 256 (2019) ), especially the carrier conduction mechanism is related to dielectric film defects such as grain boundaries, internal impurities (oxygen deficiency, etc.), and external impurities incorporated into the thin film during the deposition process. It is known that the bulk properties of

Therefore, rather than using a different high dielectric material or a metal electrode having a different work function, a technique for reducing the cause of defects in bulk ZrO ₂ and HfO ₂ is effective.

The thin film according to the present invention improves film quality and film conformality through a bottom-up thin film composition containing organic pulses that do not remain in the thin film, while reducing leakage current, and improving reliability of semiconductor devices. It is intended to secure even at a low temperature such as 250 ℃.

The purpose of the present invention is to provide a conformal thin film in a bottom-up method by lowering the growth rate even when a thin film is formed on a substrate having a complicated structure, while reducing leakage current by reducing impurities in the thin film and greatly improving the density of the thin film. to be

In addition, an object of the present invention is to secure the reliability of a semiconductor device by providing a film quality of a thin film having a high dielectric constant (high-k) under low temperature conditions.

In order to achieve the above object, the present invention provides a bottom up thin film composition including a pulse precursor.

The pulse precursor may be a hybrid precursor including an inorganic precursor and an organic precursor.

The inorganic precursor is Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, The group consisting of Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn It may include one or more selected from.

The inorganic precursor is represented by Formula 2a

[Formula 2a]

(The M ₁ is Zr, Hf, Si, Ge or Ti, the X ₁ , X ₂ , X ₃ are independently -NR ₁ R ₂ or -OR ₃ , and the R ₁ to R ₃ independently have 1 carbon atom to 6 alkyl groups, wherein n is 1 or 2);

Formula 2b

[Formula 2b]

(Wherein M is Zr, Hf, Si, Ge or Ti, R ₁ is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' ₁ , X' ₂ and X' ₃ is independently -NR ₁ R ₂ or -OR ₃ , and R' ₁ to R' ₃ are independently an alkyl group having 1 to 6 carbon atoms.); and

Formula 2c

[Formula 2c]

(Wherein M1 is Zr, Hf, Si, Ge or Ti, X ¹¹ and X ¹² are each independently an alkyl group or any one selected from the group consisting of -NR ₃ R ₄ and -OR ₅ , wherein R1 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, and n ¹ and n ² are each independently an integer of 0 to 5.) may be one or more thin film residual precursors selected from the group consisting of compounds represented by .

The organic precursor is represented by Formula 1

[Formula 1]

AnBmXoYiZj

(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1, wherein i and j are integers from 0 to 3).

The organic precursor may be a compound having a purity of 99.9% or more.

The organic precursor may be a precursor that does not remain in the thin film.

The inorganic precursor and the organic precursor may have a weight ratio of 1:99 to 99:1.

The composition may include a reactant gas pulse.

The reaction gas pulse may be an oxidizing agent pulse, a nitrifying agent pulse or a reducing agent pulse.

In addition, the present invention deposits a bottom-up thin film composition containing a pulse precursor into a chamber and deposited on a loaded substrate surface, wherein the pulse precursor includes an inorganic precursor and an organic precursor,

The inorganic precursor is Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, The group consisting of Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn Including one or more selected materials from,

The organic precursor is represented by Formula 1

[Formula 1]

AnBmXoYiZj

(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n + 1, and i and j are integers from 0 to 3.) In the case of a branched, cyclic or aromatic compound represented by

It provides a bottom-up thin film formation method comprising the step of bottom-up depositing the inorganic precursor on the substrate.

The substrate may have an aspect ratio of 10:1 or greater.

The bottom-up depositing of the inorganic precursor on the substrate may include injecting and purging the organic precursor pulse onto the substrate; injecting and purging the organic precursor pulse onto a substrate; and injecting and purging a reactive gas pulse onto the substrate.

The bottom-up depositing of the inorganic precursor on the substrate may include injecting and purging the inorganic precursor pulse onto the substrate; injecting and purging the organic precursor pulse onto a substrate; and injecting and purging a reactive gas pulse onto the substrate.

The bottom-up depositing of the inorganic precursor on the substrate may include injecting and purging the organic precursor pulse onto the substrate; injecting and purging the organic precursor pulse onto a substrate; Injecting and purging a reaction gas pulse onto the substrate; and injecting and purging the organic precursor pulse onto the substrate.

The bottom-up depositing of the inorganic precursor on the substrate may include co-injecting and purging the inorganic precursor and the organic precursor on the substrate; and injecting and purging a reactive gas pulse onto the substrate.

The bottom-up thin film forming method may be performed at 200 to 500 °C.

The reaction gas pulse may use a pulse of an oxidizing agent, a reducing agent, or a nitriding agent.

The method of forming the bottom-up thin film may be performed by atomic layer deposition or chemical vapor deposition.

The bottom-up thin film may be a metal oxide thin film, a metal nitride thin film, a metal thin film, or a thin film in which two or more of these thin films have selective regions.

In addition, the present invention provides a semiconductor substrate characterized in that it is manufactured by the method of forming the bottom-up thin film described above.

The semiconductor substrate includes low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, and a DRAM trench capacitor. , 3D Gate-All-Around (GAA) or 3D NAND.

In addition, the present invention provides a semiconductor device comprising the semiconductor substrate described above.

According to the present invention, there is an effect of providing a bottom-up thin film composition that provides a conformal thin film in a bottom-up method even when a thin film is formed on a substrate having a complicated structure.

According to the present invention, there is an effect of providing a thin film composition that improves the quality of a thin film by more effectively removing process by-products when forming a bottom-up thin film, reducing the deposition rate to appropriately lower the thin film growth rate, and improving the crystallinity of the thin film.

According to the present invention, it is possible to provide a bottom-up thin film composition that reduces leakage current caused by oxidation of a lower electrode in a conventional high-temperature process by reducing impurities in a bottom-up thin film and greatly improving the density of the thin film. There is an effect of providing a thin film formation method and a semiconductor device manufactured therefrom.

1 is a diagram schematically showing a thin film manufacturing cycle using a bottom-up thin film composition according to the present invention, and the left figure shows a bottom-up thin film manufacturing cycle (hereinafter, a first process) in which an organic precursor is added and then an inorganic precursor is added in the bottom-up thin film composition. Also referred to as), the right figure shows a bottom-up thin film manufacturing cycle (hereinafter also referred to as a second process) of adding an organic precursor after adding an inorganic precursor in the bottom-up thin film composition.
2 is a GPC analysis graph showing deposition rates of bottom-up thin films of Examples 1 to 3 and Examples 6 to 8 of the present invention and bottom-up thin films of Comparative Examples 1 to 6 (Ref. HfO ₂ ).
Figure 3 is a 200 nm lower point from the top and bottom of the HfO ₂ thin film deposited according to Example 1 and Comparative Example 1 of the present invention at 320 ° C. on a substrate having a trench structure with an aspect ratio (length / diameter) of 22.6: 1 It is a TEM picture of a cross section at a point above 100 nm.
FIG. 4 shows deposition temperatures of 320° C. (a diagram, Example 1 and Comparative Example 1), 300° C. (b diagram, Example 2 and Comparative Example 2), and 250° C. (c diagram, Example 3 and Comparative Example 3). It is a SIMS analysis graph showing the reduction rate of carbon (C) and iodine (I) elements according to the depth of the bottom-up thin film manufactured by
5 is a film density analysis graph of bottom-up thin films prepared at deposition temperatures of 320 ° C, 300 ° C, and 250 ° C of Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention.
6 is an XPS analysis graph confirming the component content (atomic %) according to the depth of the bottom-up thin film prepared at a deposition temperature of 250° C. in Example 3 and Comparative Example 3 of the present invention.
7 is an XRD pattern analysis graph of bottom-up thin films prepared at a deposition temperature of 250° C. in Example 3, Comparative Examples 1 and 3 of the present invention.

Hereinafter, the bottom-up thin film composition of the present disclosure, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom will be described in detail.

As used herein, the term "bottom up" refers to growth from the bottom of a substrate having a trench structure, unless otherwise specified, wherein the substrate having a trench structure has, for example, an aspect ratio of 10:1 or greater. , or 20:1 or greater.

The aspect ratio refers to the ratio of length/diameter (L/D) of the trench structure, unless otherwise specified, where length and diameter respectively define portions commonly referred to in the art.

The present inventors use a bottom-up growth composition including a pulsed precursor including an inorganic precursor and an organic precursor and a reactive gas pulse on the surface of a substrate loaded into a chamber to form a bottom-up thin film at a low temperature such as 250 ° C. As a result, it was confirmed that the top and bottom growth rates of the bottom-up thin film formed after deposition were greatly reduced, and as a result, the conformal characteristics were greatly improved in a trench structure with a high aspect ratio. In addition, contrary to expectations, it was confirmed that the residual amount of carbon and iodine was reduced, and the density and impurities of the thin film were greatly improved. Based on this, further research was conducted and the present invention was completed.

In a preferred embodiment of the thin film forming method, a bottom up thin film composition including a pulse precursor is injected into a chamber and deposited on a loaded substrate surface, wherein the pulse precursor comprises an inorganic precursor and An organic precursor may be included, and the inorganic precursor and the organic precursor may be simultaneously injected onto a substrate and then deposited by injecting a reaction gas pulse. In this case, the thin film growth rate is appropriately lowered and the deposition temperature during thin film formation Even if is lowered, the density, crystallinity, conformal characteristics, and dielectric characteristics of the bottom-up thin film are improved, and the leakage current is effectively reduced, so that the film quality is greatly improved.

In another preferred embodiment, the thin film forming method includes vaporizing an inorganic precursor and an organic precursor separately or simultaneously and adsorbing the inorganic precursor and the organic precursor to the surface of the loaded substrate in the chamber; purging the inside of the chamber with a purge gas; supplying a reaction gas into the chamber; and purging the inside of the chamber with a purge gas.

In another preferred embodiment of the thin film forming method, a bottom up thin film composition including a pulse precursor is injected into a chamber and deposited on a loaded substrate surface, wherein the pulse precursor is an inorganic precursor. and an organic precursor, injecting and purging the organic precursor onto the substrate; purging the substrate by injecting the inorganic precursor; and purging the substrate by injecting a pulse of a reaction gas onto the substrate and depositing the inorganic precursor. Crystallinity, conformal characteristics, and dielectric characteristics are improved, and leakage current is effectively reduced, so that film quality is greatly improved.

In another preferred embodiment of the thin film forming method, a bottom up thin film composition including a pulse precursor is injected into a chamber and deposited on a loaded substrate surface, wherein the pulse precursor is an inorganic precursor. and an organic precursor, injecting and purging the inorganic precursor onto the substrate; purging by injecting the organic precursor onto the substrate; and purging the substrate by injecting a pulse of a reaction gas onto the substrate and depositing the inorganic precursor. Crystallinity, conformal characteristics, and dielectric characteristics are improved, and leakage current is effectively reduced, so that film quality is greatly improved.

In another preferred embodiment of the thin film forming method, a bottom up thin film composition including a pulse precursor is injected into a chamber and deposited on a loaded substrate surface, wherein the pulse precursor is an inorganic precursor. and an organic precursor, injecting and purging the organic precursor onto the substrate; purging the substrate by injecting the inorganic precursor; purging the substrate by injecting a reaction gas pulse and depositing the inorganic precursor; and purging by injecting the organic precursor onto the substrate. In this case, even if the thin film growth rate is appropriately lowered and the deposition temperature is lowered during thin film formation, the density, crystallinity, and conformal characteristics of the bottom-up thin film There is an advantage in that the dielectric properties are improved and the leakage current is effectively reduced, so that the film quality is greatly improved.

The thin film manufactured by the thin film forming method may be a bottom-up thin film, and the inorganic precursor remains and is deposited to form a thin film in the thin film, but the organic precursor does not remain.

The inorganic precursor, the organic precursor, the reaction gas, and the gas used for the purge may be independently transferred into the chamber preferably by a VFC method, a DLI method, or an LDS method, and more preferably transferred into the chamber by an LDS method. .

The chamber may be a CVD chamber or an ALD chamber, but is not limited thereto.

In one embodiment of the present invention, the bottom-up thin film composition may include a pulse precursor.

In the present invention, a pulse precursor refers to a precursor that can be supplied in a pulse phase using a Vapor Flow Controller (VFC) and/or a Liquid Delivery System (LDS), wherein the pulse phase is a pulse commonly used in the art. state is free

The pulse precursor may be, for example, a hybrid precursor including an inorganic precursor and an organic precursor.

The inorganic precursor used in the present invention refers to a material that remains in the bottom-up thin film and can help improve conductivity, and may be, for example, a material represented by Chemical Formula 2 below.

[Formula 2]

M _x L _y

(wherein x is an integer from 1 to 3, and M is Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, It may be selected from the group consisting of Bi, Pt, At and Tn, wherein y is an integer from 1 to 6, and L is each independently H, C, N, O, F, P, S, Cl, Br or I, or a ligand consisting of a combination of two or more selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br), in this case, the desired effect of the present invention is well expressed and high permittivity has the advantage of having

As a preferred embodiment, the inorganic precursor is represented by the following formula (2a)

[Formula 2a]

(The M ₁ is Zr, Hf, Si, Ge or Ti, the X ₁ , X ₂ , X ₃ are independently -NR ₁ R ₂ or -OR ₃ , and the R ₁ to R ₃ independently have 1 carbon atom to 6 alkyl groups, wherein n is 1 or 2);

Formula 2b

[Formula 2b]

(Wherein M is Zr, Hf, Si, Ge or Ti, R ₁ is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' ₁ , X' ₂ and X' ₃ is independently -NR ₁ R ₂ or -OR ₃ , and R' ₁ to R' ₃ are independently an alkyl group having 1 to 6 carbon atoms.); and

Formula 2c

[Formula 2c]

(Wherein M1 is Zr, Hf, Si, Ge or Ti, X ¹¹ and X ¹² are each independently an alkyl group or any one selected from the group consisting of -NR ₃ R ₄ and -OR ₅ , wherein R1 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, and n ¹ and n ² are each independently an integer of 0 to 5). It is preferred in terms of stability and reactivity.

The organic precursor used in the present invention refers to a non-residual material in the bottom-up thin film having substantially no reactivity with the inorganic precursor, and may be, for example, a material represented by Chemical Formula 1 below.

[Formula 1]

AnBmXoYiZj

(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n + 1, wherein i and j are integers from 0 to 3), characterized in that they are branched, cyclic or aromatic compounds represented by, in this case, they act as a precursor that does not remain in the thin film. The effect is well expressed and has the advantage of having a high permittivity.

As used herein, the term "non-remaining" refers to the case where the C element is present at less than 0.1 atomic % and the N element is present at less than 0.1 atomic % upon component analysis by XPS, unless otherwise specified.

The organic precursor may preferably be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. It is better to use more than one material.

The inorganic precursor and the organic precursor have a weight ratio of 1: 99 to 99: 1, a weight ratio of 1: 90 to 90: 1, a weight ratio of 1: 85 to 85: 1, or a weight ratio of 1: 80 to 80: 1 it could be

The composition includes a reactant gas pulse, which may be a pulse of an oxidizing agent, a nitrifying agent, or a reducing agent.

The oxidizing agent, nitriding agent, and reducing agent may be materials commonly used in the art. For example, the oxidizing agent is O ₃ , O ₂ or a mixture thereof, and the nitriding agent is NH ₃ , N ₂ H ₂ , N ₂ or any of these. Mixing, the reducing agent may be H ₂ and the like, but is not limited thereto.

In a preferred embodiment of the thin film formation method of the present invention, a bottom-up thin film composition including the pulse precursor is injected into a chamber and adsorbed on the surface of a loaded substrate, wherein the pulse precursor includes an inorganic precursor and an organic precursor. In this case, the thin film growth rate is appropriately increased, and process by-products generated during thin film formation are effectively removed, so that even if the deposition temperature is reduced, impurities in the thin film are reduced and crystallinity is greatly improved.

The thin film forming method uses the aforementioned reducing agent, nitriding agent, or oxidizing agent as a reaction gas.

In another preferred embodiment of the thin film formation method of the present invention, a bottom up thin film composition including a pulse precursor is injected into a chamber and deposited on a loaded substrate surface,

The pulse precursor includes an inorganic precursor and an organic precursor,

The inorganic precursor is Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, The group consisting of Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn At least one material selected from,

The organic precursor is represented by Formula 1

[Formula 1]

AnBmXoYiZj

(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1, where i and j are integers from 0 to 3), including bottom-up deposition of the inorganic precursor and the organic precursor in the case of a branched, cyclic or aromatic compound represented by to be characterized

In the bottom-up thin film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may include, for example, injecting and purging the organic precursor pulse onto the substrate; injecting and purging the inorganic precursor pulse onto a substrate; and injecting and purging a reactive gas pulse onto the substrate.

Further, in the bottom-up thin film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may include, for example, injecting and purging the inorganic precursor pulse onto the substrate; injecting and purging the organic precursor pulse onto a substrate; and injecting and purging a reactive gas pulse onto the substrate.

Further, in the method of forming a bottom-up thin film of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may include, for example, injecting and purging the organic precursor pulse onto the substrate; injecting and purging the inorganic precursor pulse onto a substrate; Injecting and purging a reaction gas pulse onto the substrate; and injecting and purging organic precursor pulses on the substrate.

Furthermore, in the bottom-up thin film formation method of the present invention, the step of bottom-up depositing the inorganic precursor on the substrate may include, for example, simultaneously injecting and purging the inorganic precursor pulse and the organic precursor pulse on the substrate; and injecting and purging a reactive gas pulse onto the substrate.

In the bottom-up thin film formation method, the deposition temperature is, for example, 200 to 500 ° C, preferably 250 to 450 ° C, and specific examples are 250 to 420 ° C, 250 to 320 ° C, 380 to 420 ° C, or 400 to 450 ° C, , there is an advantage in that thin film quality and step coverage are greatly improved within this range.

In the method of forming a bottom-up thin film, for example, a reducing agent, a nitriding agent, or an oxidizing agent may be used as a reaction gas, and different reaction gases may be applied to a partially selected area and the remaining areas, respectively, if necessary.

The method of forming the bottom-up thin film may be performed by, for example, atomic layer deposition or chemical vapor deposition, and, if necessary, plasma atomic layer deposition or plasma chemical vapor deposition.

The method of forming the thin film may be, for example, a metal oxide thin film, a metal nitride thin film, or a metal thin film, and if necessary, two or more of these thin films may be thin films having selective regions.

According to one embodiment of the present invention, it is possible to provide a semiconductor substrate characterized in that manufactured by the above-described thin film forming method.

The semiconductor substrate includes low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, and a DRAM trench capacitor. , 3D Gate-All-Around (GAA) or 3D NAND.

Furthermore, according to another embodiment of the present invention, it is possible to provide a semiconductor device characterized by including the above-described semiconductor substrate.

For example, in the manufacture of a capacitor including a bottom-up thin film according to the present invention, two to three or more layers may be stacked and provided. In this case, inorganic precursors constituting each layer may be stacked in different types, but if necessary Therefore, it is also possible to laminate using the same type.

For example, a capacitor may be formed by sequentially forming a lower electrode, a dielectric film, and a second electrode on a semiconductor substrate.

In this case, the lower electrode may be a storage electrode of a DRAM device or other device or an electrode of a decoupling capacitor.

For example, the lower electrode may be manufactured in a cylinder shape or a pillar shape capable of securing a large surface area, and may be formed of a conductive layer or a metal layer.

The dielectric film may be a metal oxide film, and when deposited using the bottom-up thin film composition according to the present invention, even thickness and appropriate adhesion are advantageous even when formed on a lower step or a lower electrode having a topology. have.

An upper electrode formed on the dielectric layer may be formed of the same conductive layer or metal layer as the lower electrode.

Hereinafter, preferred embodiments and drawings are presented to aid understanding of the present invention, but the following embodiments and drawings are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention to those skilled in the art. It is obvious in this regard, and it is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

Example 1

An HfO ₂ bottom-up thin film was deposited on a SiO 2 substrate having a trench structure with an aspect ratio of 22.6:1 (length:diameter) using the thin film fabrication cycle shown in the left side of FIG. 1 below.

The drawing on the left side of FIG. 1 corresponds to an experiment in which pulses of organic precursors are added followed by pulses of inorganic precursors in the bottom-up thin film composition according to the present invention, and is referred to as a first process.

Specifically, a cycle of injecting an organic precursor pulse for 3 seconds and then purging for 6 seconds, injecting an inorganic precursor pulse for 3 seconds and then purging for 6 seconds, then injecting a reaction gas pulse for 3 seconds and purging for 6 seconds is included.

The aforementioned HfO ₂ bottom-up thin film was deposited in a 12-inch ALD system equipped with a shower head.

As the inorganic precursor, CpHf, a compound represented by Formula 3-1 below, was prepared. The CpHf was purchased from Sigma and used without purification.

[Formula 3-1]

As the organic precursor, TBI, a compound represented by Formula 3-2 below, was prepared. The TBI was synthesized by the applicant and purified to 99.9% purity before use.

[Formula 3-2]

The prepared organic precursor was placed in a canister and supplied to a vaporizer heated to 90° C. at a flow rate of 0.01 g/min using a Liquid Mass Flow Controller (LMFC) at room temperature. The prepared CpHf was put in a separate canister and supplied to a separate vaporizer heated to 170° C. at a flow rate of 0.1 g/min.

The organic precursor vaporized in vapor phase in a vaporizer is injected into a deposition chamber loaded with a substrate in which TiN is grown to a thickness of 20 nm on top of which 100 nm of SiO2 has been grown on a Si wafer for 3 seconds, and then argon gas is supplied at 300 sccm for 6 seconds. argon purging was performed. A substrate on which a metal oxide film is to be formed was heated to 320° C., and at this time, the pressure in the reaction chamber was controlled to 0.74 Torr.

Next, CpHf vaporized in a vaporizer was introduced into the deposition chamber for 3 seconds, and argon purging was performed by supplying argon gas at 300 sccm for 6 seconds. A substrate on which a metal oxide film is to be formed was heated to 320° C., and at this time, 0.74 Torr was controlled in the reaction chamber.

Subsequently, 1000 sccm of ozone as a reactive gas was introduced into the reaction chamber for 3 seconds, followed by argon purging for 6 seconds. A substrate on which a metal oxide film is to be formed was heated to 320° C., and at this time, 0.74 Torr was controlled in the reaction chamber.

This process was repeated 100 times to form a self-limiting atomic layer HfO ₂ thin film.

Example 2

An HfO ₂ thin film was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 300 °C in Example 1.

Example 3

A HfO ₂ thin film was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 250 °C in Example 1.

Example 4

In Example 1, the inorganic precursor was replaced with TEMAHf (Tetrakis (ethylmethylamino) Hafniumb), a compound represented by Formula 3-3 below. A self-limiting atomic layer HfO ₂ thin film was formed in the same manner as in Example 1 except for the above.

[Formula 3-3]

Example 5

In Example 1, the organic precursor was replaced with TBB, a compound represented by Formula 3-4 below. A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 1 except for the above. The TBB was synthesized by the applicant and purified to 99.9% purity before use.

[Formula 3-4]

Example 6

The same process as in Example 1 was repeated except that the thin film manufacturing cycle shown in the left drawing of FIG. 1 used in Example 1 was changed to the thin film manufacturing cycle shown in the right drawing of FIG.

Specifically, an HfO ₂ bottom-up thin film was deposited on a SiO 2 substrate having a trench structure with an aspect ratio of 22.6:1 (length:diameter) using the thin film manufacturing cycle shown in the right side of FIG. 1 .

The drawing on the right side of FIG. 1 corresponds to an experiment in which pulses of inorganic precursors are added followed by pulses of organic precursors in the bottom-up thin film composition according to the present invention, and is referred to as a second process.

Specifically, a cycle of injecting an inorganic precursor pulse for 3 seconds and then purging for 6 seconds, injecting an organic precursor pulse for 3 seconds and purging for 6 seconds, then injecting a reaction gas pulse for 3 seconds and purging for 6 seconds is included. A substrate on which a metal oxide film is to be formed was heated to 320° C., and at this time, 0.74 Torr was controlled in the reaction chamber.

Example 7

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 300 °C.

Example 8

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 6, except that the heating temperature of the substrate was adjusted to 250 °C.

Example 9

In Example 1, the inorganic precursor was replaced with CpZr, which is a compound represented by Formula 3-5, and the organic precursor was added at a flow rate of 0.1 g/min, and the heating temperature of the substrate was adjusted to 320 ° C. A ZrO ₂ thin film as a self-limiting atomic layer was formed in the same manner.

[Formula 3-5]

Example 10

A ZrO ₂ thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that the heating temperature of the substrate was adjusted to 300 °C.

Example 11

A ZrO ₂ thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that the heating temperature of the substrate was adjusted to 250 °C in Example 9.

Example 12

In Example 6, the inorganic precursor was replaced with CpZr, which is a compound represented by Formula 3-5, and the organic precursor was added at a flow rate of 0.1 g/min, and the heating temperature of the substrate was adjusted to 320 ° C. A ZrO ₂ thin film as a self-limiting atomic layer was formed in the same manner.

Example 13

A ZrO ₂ thin film as a self-limiting atomic layer was formed in the same manner as in Example 12, except that the heating temperature of the substrate was adjusted to 300 °C.

Example 14

A ZrO ₂ thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 12, except that the heating temperature of the substrate was adjusted to 250 °C.

Comparative Example 1

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 1, except that the organic precursor was not added in Example 1.

Comparative Example 2

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 2, except that the organic precursor was not added in Example 2.

Comparative Example 3

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 3, except that the organic precursor was not added in Example 3.

Comparative Example 4

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 6, except that the organic precursor was not added in Example 6.

Comparative Example 5

A self-limiting atomic layer, HfO ₂ thin film, was formed in the same manner as in Example 7, except that the organic precursor was not added in Example 7.

Comparative Example 6

A self-limiting atomic layer, ZrO ₂ thin film, was formed in the same manner as in Example 8, except that the organic precursor was not added in Example 8.

Comparative Example 7

A self-limiting atomic layer, ZrO ₂ thin film, was formed in the same manner as in Example 9, except that the organic precursor was not added in Example 9.

Comparative Example 8

A self-limiting atomic layer, ZrO ₂ thin film, was formed in the same manner as in Example 9, except that the organic precursor was not added in Example 10.

Comparative Example 9

A ZrO ₂ thin film, which is a self-limiting atomic layer, was formed in the same manner as in Example 9, except that the organic precursor was not added in Example 11.

[Experimental example]

1) Deposition evaluation

In Examples 1 to 3 and 5 to 6 and Comparative Examples 1 to 4, the inorganic precursor was CpHf, in Example 4 and Comparative Example 5, the inorganic precursor was TEMAHf, and in Examples 7 to 10 and Comparative Examples 6 to 7, inorganic The experiment was conducted by changing the precursor to CpZr. Overall, the deposition rate decreased when the organic precursor was added before the inorganic precursor, and the deposition rate tended to increase when the organic precursor was added later than the inorganic precursor (Table 1 and below). see Figure 2).

As shown in Examples 1 to 6 and Comparative Examples 1 to 3, the tendency was greater in the case of low temperature. In addition, as shown in Examples 1 to 8, Comparative Examples 1 to 3, Examples 9 to 14, and Comparative Examples 5 to 6, this tendency was greater in the case of the ZrO ₂ thin film.

division organic precursors inorganic precursors Deposition rate (Å/cycle) Example 1 Tert-butyl iodide CpHf 0.564 Example 2 Tert-butyl iodide CpHf 0.583 Example 3 Tert-butyl iodide CpHf 0.628 Example 6 Tert-butyl iodide CpHf 0.845 Example 7 Tert-butyl iodide CpHf 0.849 Example 8 Tert-butyl iodide CpHf 0.942 Example 9 Tert-butyl iodide CpZr - Example 10 Tert-butyl iodide CpZr 0.643 Example 11 Tert-butyl iodide CpZr 0.705 Example 12 Tert-butyl iodide CpZr - Example 13 Tert-butyl iodide CpZr 0.870 Example 14 Tert-butyl iodide CpZr 0.896 Comparative Example 1 unused CpHf 0.716 Comparative Example 2 unused CpHf 0.712 Comparative Example 3 unused CpHf 0.685 Comparative Example 5 unused CpZr 0.755 Comparative Example 6 unused CpZr 0.737

2) Impurity reduction characteristics

The C reduction rate (%) was calculated by Equation 2 below.

[Equation 2]

C reduction rate = {(Comparative Example 1 SIMS C intensity - Example SIMS C intensity) / Example SIMS C intensity } x 100

As can be seen in FIG. 4, Examples 1 to 3 using an inorganic precursor as a Hf thin film precursor while using an organic precursor according to the present invention are thinner than Comparative Example 1 (Ref HfO ₂ ) without using an organic precursor. It was confirmed that the C intensity, which is an anti-contaminant, was greatly reduced, and the impurity reduction property was very excellent.

More specifically, Example 1 (corresponding to FIG. 4 (a)) using CpHf as an inorganic precursor at 320 ° C., compared to Comparative Example 1 (C (Counts / s) = 8227) as a control, CpHf as a contaminant in the thin film The strength decreased by 76%, and Example 2 using CpHf as an inorganic precursor at 300 ° C. (corresponding to FIG. 4 (b)) showed a 66% decrease in C intensity, which is a contaminant in the thin film, compared to Comparative Example 2, which is a control group, and an inorganic precursor Example 3 using CpHf at 250 ° C. (corresponding to FIG. 4 (c)) showed a 40% decrease in C intensity, which is a contaminant in the thin film, compared to Comparative Example 3 (C (Counts / s) = 13745), which is a control group. It was confirmed once again that the Hf thin film according to the present invention had excellent impurity reduction characteristics.

In addition, the component content (atomic %) according to the depth of the bottom-up thin film prepared at the deposition temperature of 250 ° C. in Example 3 and Comparative Example 3 of the present invention was confirmed through XPS analysis, and the results are shown in FIG. showed up

The left figure of FIG. 6 is an XPS analysis graph of Comparative Example 3, and the right figure is an XPS analysis graph of Example 3. From these graphs, significant reductions in N, O, and S could be further confirmed.

3) thin film density

As shown in FIG. 5, Example 2 (thin film density 9.40 g/cm ³ ) and Example 3 (thin film density 8.0 g/cm ³ ) are Comparative Example 2 (9.0 g/cm ³ ) corresponding to their respective references. and Comparative Example 3 (7.7 g/cm ³ ), it was confirmed that the thin film density measured based on X-ray reflectometry (XRR) analysis greatly increased compared to that of Comparative Example 3 (7.7 g/cm 3 ).

From this, it can be seen that the Hf and Zr thin films according to the present invention can improve crystallinity and finally improve electrical characteristics in an integrated structure having a high aspect ratio, such as DRAM capacitance.

7 nm thick XRD patterns deposited in Examples 1 and 3 described above are shown in FIG. 7 . As shown in FIG. 7 below, amorphous as indicated by a very weak diffraction pattern was observed, and no phase transition to a crystalline phase was observed at 320 degrees. For reference, since most of the very thin deposited thin films are known to be in an amorphous state, it was confirmed that an appropriate thin film was fabricated.

4) Capacitance

The capacitance of each of the HfO ₂ thin films prepared in Example 1 and Comparative Example 1 was measured.

Specifically, metal thin films were formed on the top and bottom of the dielectric film to be measured, the top and bottom metals were electrically connected to each other, and measured using CV measurement equipment at a frequency of 1 MHz, and shown in Table 2 below.

5) Leakage current

Leakage current for each of the HfO ₂ thin films prepared in Example 1 and Comparative Example 1 was measured at 3MV/cm.

Specifically, I-V Parameter Analyzer (model: 4200-SCS; manufacturer: KEITHLEY) was measured in the Voltage Sweep Mode (0-15V) method and shown in Table 2 below.

6) dielectric constant

The dielectric constants of the HfO ₂ thin films prepared in Example 1 and Comparative Example 1, respectively, were measured.

Specifically, using a C-V Parameter Analyzer (model: E4980A, LCR Meter: 20 Hz to 2 MHz, manufacturer: KEYSIGHT) equipment, the DC-Bias Sweep Mode was measured and shown in Table 2 below.

division Capacitance (F) Leakage current (A/cm ² ) dielectric constant Example 1 2.67 x 10 ^-10 5.18 x 10 ^-8 15.1 Comparative Example 1 2.54 x 10 ^-10 1.13 x 10 ^-6 14.4

As shown in Table 2, Example 1 using the organic precursor according to the present invention was compared to Comparative Example 1 without using the organic precursor, the dielectric constant and capacitance were improved, and the leakage current was significantly reduced. there was.

Specifically, in the case of leakage current, an improvement equivalent to 95% was confirmed as 5.18 x 10 ^-8 A/cm ² , which is lower than the DRAM leakage current limit. It is believed to be caused by

7) Bottom-up conformal characteristics

The bottom-up conformal characteristics of the HfO ₂ thin films prepared in Example 1 and Comparative Example 1, respectively, were confirmed.

Specifically, HfO ₂ thin films were deposited on a substrate having a trench structure with an aspect ratio (length/diameter) of 22.6:1 at 320° C. according to Example 1 and Comparative Example 1 of the present invention.

Metal thin films were formed on the top and bottom of the HfO2 thin film, and TEM images of cross sections at 200 nm below the top and 100 nm above the bottom are shown in FIG. 3 below.

As shown in FIG. 3, Example 1 using the organic precursor according to the present invention showed a conformal property of 97% with a top thickness of 5.17 nm and a bottom thickness of 4.99 nm, whereas Comparative Example 1 without using the same had a top thickness of 7.98 nm. nm and bottom thickness of 6.96 nm, showing 87% conformal properties, it was confirmed that the improved bottom-up conformal properties.

These results according to the present invention provide strong evidence for the promising ability of hybrid precursor pulses in ALD to achieve good film quality, high film conformality and excellent electrical performance.

The innovative approach to co-precursor pulses in the ALD process of the present invention is based on low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors for future technology nodes. (high aspect ratio 3D metal-insulator-metal capacitor), DRAM trench capacitor, etc., and other 3D devices such as 3D Gate-All-Around (GAA) and 3D NAND. The architecture can provide a variety of opportunities.

Claims (20)

A bottom up thin film composition comprising a pulse precursor. According to claim 1,
The bottom up thin film composition, characterized in that the pulse precursor is a hybrid precursor pulse comprising an inorganic precursor and an organic precursor. According to claim 2,
The inorganic precursor is Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, The group consisting of Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn A bottom-up thin film composition comprising at least one selected from According to claim 3,
The inorganic precursor is represented by Formula 2a
[Formula 2a]

(The M ₁ is Zr, Hf, Si, Ge or Ti, the X ₁ , X ₂ , X ₃ are independently -NR ₁ R ₂ or -OR ₃ , and the R ₁ to R ₃ independently have 1 carbon atom to 6 alkyl groups, wherein n is 1 or 2);
Formula 2b
[Formula 2b]

(Wherein M is Zr, Hf, Si, Ge or Ti, R ₁ is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' ₁ , X' ₂ and X' ₃ is independently -NR ₁ R ₂ or -OR ₃ , and R' ₁ to R' ₃ are independently an alkyl group having 1 to 6 carbon atoms.); and
Formula 2c
[Formula 2c]

(Wherein M1 is Zr, Hf, Si, Ge or Ti, X ¹¹ and X ¹² are each independently an alkyl group or any one selected from the group consisting of -NR ₃ R ₄ and -OR ₅ , wherein R1 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, and n ¹ and n ² are each independently an integer of 0 to 5.) characterized in that at least one thin film residual precursor selected from the group consisting of compounds represented by Bottom-up thin film composition to be. According to claim 2,
The organic precursor is represented by Formula 1
[Formula 1]
AnBmXoYiZj
(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1, wherein i and j are integers from 0 to 3), and is a branched, cyclic or aromatic compound represented by
The bottom-up thin film composition, characterized in that the organic precursor is a precursor that does not remain in the thin film. According to claim 2,
The bottom-up thin film composition, characterized in that the inorganic precursor and the organic precursor have a weight ratio of 1: 99 to 99: 1. According to claim 1,
The bottom-up thin film composition, characterized in that the composition includes a reaction gas pulse, wherein the reaction gas pulse is a pulse of an oxidizing agent, a nitriding agent, or a reducing agent. A bottom up thin film composition containing a pulse precursor is injected into the chamber and deposited on the loaded substrate surface,
The pulse precursor includes an inorganic precursor and an organic precursor,
The inorganic precursor is Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, The group consisting of Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn Including one or more selected materials from,
The organic precursor is represented by Formula 1
[Formula 1]
AnBmXoYiZj
(A is carbon or silicon, B is hydrogen or alkyl having 1 to 3 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), , wherein Y and Z are independently one or more selected from the group consisting of oxygen, nitrogen, sulfur and fluorine and are not the same, n is an integer from 1 to 15, o is an integer of 1 or more, and m is 0 to 2n + 1, and i and j are integers from 0 to 3.) In the case of a branched, cyclic or aromatic compound represented by
A method of forming a bottom-up thin film, comprising bottom-up depositing the inorganic precursor on the substrate. According to claim 8,
The method of forming a bottom-up thin film, characterized in that the substrate has an aspect ratio of 10: 1 or more. According to claim 8,
Bottom-up depositing the inorganic precursor on the substrate,
injecting and purging the organic precursor pulse onto a substrate;
injecting and purging the inorganic precursor pulse onto a substrate; and
A method of forming a bottom-up thin film, comprising the steps of injecting and purging a reactive gas pulse onto a substrate. According to claim 8,
Bottom-up depositing the inorganic precursor on the substrate,
injecting and purging the inorganic precursor pulse onto a substrate;
injecting and purging the organic precursor pulse onto a substrate; and
A method of forming a bottom-up thin film, comprising injecting and purging a reactive gas pulse onto the substrate. According to claim 8,
Bottom-up depositing the inorganic precursor on the substrate,
injecting and purging the organic precursor pulse onto a substrate;
injecting and purging the inorganic precursor pulse onto a substrate;
injecting and purging a reaction gas pulse onto the substrate; and
The method of forming a bottom-up thin film, comprising injecting and purging the organic precursor pulse onto the substrate. According to claim 8,
Bottom-up depositing the inorganic precursor on the substrate,
co-injecting and purging the inorganic precursor and the organic precursor onto a substrate; and
A method of forming a bottom-up thin film, comprising the steps of injecting and purging a reactive gas pulse onto a substrate. According to any one of claims 8 to 13,
The method of forming a bottom-up thin film, characterized in that the method of forming a bottom-up thin film is performed at 200 to 500 ° C. According to any one of claims 8 to 13,
The reaction gas pulse is a bottom-up thin film forming method, characterized in that the pulse of an oxidizing agent, reducing agent or nitriding agent. According to any one of claims 8 to 13,
The method of forming the bottom-up thin film, characterized in that the method of forming the bottom-up thin film is performed by atomic layer deposition or chemical vapor deposition. According to any one of claims 8 to 13,
Wherein the bottom-up thin film is a metal oxide thin film, a metal nitride thin film, a metal thin film, or a thin film in which two or more of these thin films have a selective region. A semiconductor substrate manufactured by the method of forming a bottom-up thin film according to any one of claims 8 to 13. According to claim 18,
The semiconductor substrate includes low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, and a DRAM trench capacitor. , 3D Gate-All-Around (GAA; Gate-All-Around) or 3D NAND, characterized in that the semiconductor substrate. A semiconductor device comprising the semiconductor substrate of claim 19 .

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