Method for manufacturing thin film of tin-doped molybdenum dioxide, and capacitor using same

Abstract

The present invention relates to a capacitor electrode material, which is a component of a next generation DRAM, and a process for formation and deposition of the electrode material, and a method for manufacturing a thin film of tin-doped molybdenum dioxide, according to an embodiment of the present invention, comprises: a first step of forming molybdenum trioxide (MoO3) by injecting a molybdenum source and ozone (O3) reaction gas onto the surface of a substrate; a second step of forming an atomic layer by doping tin oxide (SnOx) on the surface of the formed molybdenum trioxide (MoO3); and a step of forming a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer by repeating the first step or the second step.

Description

Method for manufacturing tin-doped molybdenum dioxide thin film and capacitor using the same

[0001] The present invention relates to a capacitor electrode material and a deposition process for forming the electrode material, which is a component of a next-generation DRAM, and more specifically, to a technical idea for manufacturing a tin-doped molybdenum dioxide thin film using atomic layer deposition (ALD) for application to a capacitor.

[0002] As capacitors become smaller, technologies are needed to improve capacitance and suppress leakage current.

[0003] Currently, the electrode materials of capacitors are generally TiN-based upper and lower electrodes, and the dielectric film materials are ZrO2 / Al2O3 / ZrO2 or HfO2 / ZrO2-based materials. However, in the future, due to miniaturization, there are issues of increased leakage current due to a decrease in the dielectric film thickness of capacitors and decreased capacitance due to a decrease in the capacitor area. Therefore, it is necessary to develop new materials and new deposition process methods for the new materials to suppress leakage current and improve the capacitance of capacitors.

[0004] Molybdenum oxide is attracting attention as a material that can replace TiN-based electrode materials, but molybdenum trioxide (MoO3) is generally the stable phase, and most deposition techniques for molybdenum oxide are known to form molybdenum trioxide.

[0005] However, molybdenum trioxide is a non-conductive material and cannot be used as an electrode material for next-generation DRAM.

[0006] On the other hand, molybdenum dioxide (MoO2) has excellent conductivity despite being an oxide, and has a high work function and a rutile crystal structure, so when combined with titanium dioxide (TiO2), it has the advantage of being able to obtain rutile TiO2 with a high dielectric constant. Therefore, the development of a process for forming a molybdenum dioxide, i.e., MoO2 thin film is very important.

[0007] It has been known that the formation of molybdenum dioxide thin films is possible through pulse laser deposition, solution processes, etc., but in order to apply it to DRAM capacitors, it must be possible to form molybdenum dioxide using atomic layer deposition (ALD).

[0008] However, until now, an ALD process capable of stably forming molybdenum dioxide has not been developed, and most of the ALD processes developed are only for molybdenum trioxide.

[0009] That is, in recent years, there is a need to develop an atomic layer deposition process technology for depositing molybdenum dioxide.

[0010] The present invention is to obtain a MoO2 thin film composition other than ALD MoO3 by adding ALD tin oxide (SnO) to the existing ALD MoO3 process. x ) to secure the composition of MoO2.

[0011] The purpose of the present invention is to obtain a structure of a thin film formed through post-heat treatment as MoO2 in a rutile phase.

[0012] The present invention aims to form an ALD MoO2 thin film on any substrate without a TiN template effect.

[0013] The present invention aims to solve the problem of forming a TiO2 oxide film between TiN and MoO2.

[0014] The present invention relates to a method for forming ALD MoO2 using tin oxide (SnO) x ) to control composition and structure simultaneously.

[0015] A method for manufacturing a tin-doped molybdenum dioxide thin film according to an embodiment comprises the steps of: a first step of forming molybdenum trioxide (MoO3) by injecting a molybdenum source and ozone (O3) reaction gas onto the surface of a substrate; and a second step of forming tin oxide (SnO) on the surface of the formed molybdenum trioxide (MoO3). x , Tin oxide) to form an atomic layer, and a step of repeating the first or second step to form a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer.

[0016] The step of forming a thin film of tin-doped molybdenum dioxide according to one embodiment may include a step of forming a thin film of tin-doped molybdenum dioxide of 55% or less.

[0017] According to one embodiment, a heat treatment step may further be included to form a thin film of molybdenum dioxide in a rutile phase from the formed atomic layer.

[0018] The heat treatment step for forming a thin film of molybdenum dioxide in a rutile phase from the formed atomic layer according to one embodiment may include a heat treatment step at a temperature of 350°C to 600°C.

[0019] According to one embodiment, the thin film of tin-doped molybdenum dioxide on the rutile phase formed from the atomic layer may have a resistivity that is reduced compared to the resistivity before tin doping.

[0020] The step of forming a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer by repeating the first or second step according to an embodiment allows the thin film of tin-doped molybdenum dioxide to be formed regardless of the type of substrate without a template effect.

[0021] In the step of forming a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer by repeating the first or second step according to one embodiment, the surface roughness of the thin film of tin-doped molybdenum dioxide can decrease as the concentration of tin increases.

[0022] The step of forming a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer by repeating the first or second step according to one embodiment may include a step of forming an optimal thin film of tin-doped molybdenum dioxide through a tin doping ratio of 24% and a heat treatment temperature of 500°C.

[0023] A capacitor using a tin-doped molybdenum dioxide thin film according to one embodiment may include a tin-doped molybdenum dioxide (Sn-doped MoO2) thin film electrode formed on a substrate based on an atomic layer deposition (ALD) process, a dielectric layer grown in a rutile structure on the molybdenum dioxide thin film, and an electrode formed on the dielectric layer.

[0024] According to one embodiment, a tin-doped molybdenum dioxide thin film formed on the substrate is formed by injecting a molybdenum source and ozone (O3) reaction gas onto the surface of the substrate to form molybdenum trioxide (MoO3), and forming tin oxide (SnO) on the surface of the formed molybdenum trioxide (MoO3). x, Tin oxide) is doped to form an atomic layer, and by repeating the first or second step, a rutile phase can be formed from the formed atomic layer.

[0025] According to one embodiment, a tin-doped molybdenum dioxide thin film formed on the substrate comprises a process for forming molybdenum trioxide (MoO3, Molybdenum Trioxide) and forming tin oxide (SnO) on the surface of the formed molybdenum trioxide (MoO3, Molybdenum Trioxide). x , Tin oxide) can be doped to form a tin content of up to 55%.

[0026] According to one embodiment, the resistivity of a thin film of tin-doped molybdenum dioxide formed from the atomic layer on rutile after heat treatment may be reduced compared to the resistivity before tin doping.

[0027] A capacitor according to an embodiment is a process for forming the above molybdenum trioxide (MoO3) or the above tin oxide (SnO x By repeating the process of doping tin oxide (TiO2) to form an atomic layer, a thin film of tin-doped molybdenum dioxide can be formed regardless of the type of substrate without a template effect.

[0028] In one embodiment, to obtain a MoO2 thin film composition other than ALD MoO3, an ALD tin oxide (SnO) was added to the existing ALD MoO3 process. x ) can be inserted to secure the composition of MoO2.

[0029] According to one embodiment, the structure of the thin film formed through post-heat treatment can be obtained as MoO2 in rutile phase.

[0030] According to one embodiment, an ALD MoO2 thin film can be formed on all substrates without a TiN template effect.

[0031] According to one embodiment, the problem of forming a TiO2 oxide film between TiN and MoO2 can be solved.

[0032] According to one embodiment, ALD SnO is used to form ALD MoO2. x (Sn oxide) can be used to simultaneously control the composition and structure.

[0033] Figure 1 is a drawing explaining a method for manufacturing a molybdenum dioxide thin film.

[0034] Figure 2 is a diagram illustrating an atomic layer deposition process cycle for a tin-doped molybdenum dioxide thin film.

[0035] Figure 3 is a drawing explaining the composition of MoO2 obtained through the atomic layer deposition process of Figure 2 and the structure of the thin film formed through subsequent heat treatment, which is a rutile phase MoO2.

[0036] Figure 4 is a drawing explaining the template effect.

[0037] Figure 5 is a diagram showing self-limiting reactions in different precursors.

[0038] Figure 6 shows the reducing power (scavenging effect) of Sn on Mo.

[0039] Figure 7 is a drawing explaining whether TiO2 is formed between the lower layer, TiN, and MoO2.

[0040] Figure 8 shows pure Mo-O3ALD on SiO2 and Sn-doped MoO on SiO2. x This is a drawing explaining .

[0041] Figure 9 is a drawing explaining crystallization according to the position of the main peak.

[0042] Figure 10 is a drawing showing a TEM of a thin film obtained through a conventional MoO3ALD process and a TEM of a thin film obtained through a MoO2ALD process developed in the present invention.

[0043] Figure 11 is a drawing explaining the composition of a thin film according to the type of oxidizer.

[0044] Figure 12 is a diagram showing Sn concentration and resistivity for the MoO3:SnO sub-cycle ratio.

[0045] Figure 13 is a drawing showing that surface roughness decreases as the Sn composition increases.

[0046] Figure 14 is a graph showing the results of Figure 13.

[0047] Figure 15 is a drawing showing an example of forming high dielectric constant rutile TiO2 on ALD MoO2.

[0048] Figures 16 and 17 show intensity versus 2-theta [degree].

[0049] Figure 18 is a diagram showing the thickness of the oxide (EOT, Equivalent Oxide Thickness) compared to the physical thickness.

[0050] Figure 19 shows the electrical resistivity according to PDA temperature.

[0051] FIG. 20 is a drawing showing an example of forming high dielectric constant Rutile-TiO2 on ALD MoO2.

[0052] Specific structural or functional descriptions of embodiments according to the concept of the present invention disclosed in this specification are merely illustrative for the purpose of explaining embodiments according to the concept of the present invention, and embodiments according to the concept of the present invention may be implemented in various forms and are not limited to the embodiments described in this specification.

[0053] Embodiments according to the concept of the present invention may have various modifications and take various forms, and thus, embodiments are illustrated in the drawings and described in detail in this specification. However, this is not intended to limit embodiments according to the concept of the present invention to specific disclosed forms, but rather includes modifications, equivalents, or alternatives that fall within the spirit and technical scope of the present invention.

[0054] While terms such as "first" or "second" may be used to describe various components, these components should not be limited by these terms. These terms are intended solely to distinguish one component from another. For example, a first component may be referred to as a "second component," and similarly, a second component may also be referred to as a "first component," without departing from the scope of the invention.

[0055] When a component is referred to as being "connected" or "connected" to another component, it should be understood that it may be directly connected or connected to that other component, but that there may be other components in between. Conversely, when a component is referred to as being "directly connected" or "directly connected" to another component, it should be understood that there are no other components in between. Expressions that describe relationships between components, such as "between," "immediately between," or "directly adjacent to," should be interpreted similarly.

[0056] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. The singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprises" or "has" are intended to specify the presence of a described feature, number, step, operation, component, part, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0057] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and will not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0058]

[0059] Hereinafter, embodiments will be described in detail with reference to the attached drawings. However, the scope of the patent application is not limited or restricted by these embodiments. The same reference numerals in each drawing represent the same components.

[0060]

[0061] FIG. 1 is a drawing illustrating a method (100) for manufacturing a molybdenum dioxide thin film according to one embodiment.

[0062] A method for manufacturing a molybdenum dioxide thin film according to an embodiment (100) can manufacture a tin-doped molybdenum dioxide (Sn-doped MoO2) thin film based on an atomic layer deposition (ALD) process.

[0063] To this end, a method for manufacturing a molybdenum dioxide thin film according to an embodiment (100) can perform a first step of forming molybdenum trioxide (MoO3) by injecting a molybdenum source and ozone (O3) reaction gas onto a substrate surface (101).

[0064] Additionally, tin oxide (SnO) is formed on the surface of the formed molybdenum trioxide (MoO3). x , Tin oxide) can be doped to form an atomic layer (102).

[0065] In addition, the method for manufacturing a molybdenum dioxide thin film according to one embodiment (100) can form a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer by repeating the first or second step (103).

[0066] For example, a method for manufacturing a molybdenum dioxide thin film according to one embodiment (100) can form a thin film of tin-doped molybdenum dioxide by forming a tin ratio of up to 55% during the process of doping tin oxide to form an optimal thin film of tin-doped molybdenum dioxide.

[0067] The tin ratio in the process of doping tin oxide can be calculated using the following mathematical formula 1.

[0068]

[0069] [Mathematical Formula 1]

[0070] Tin ratio = [Number of tin atoms per unit volume / Sum of tin atoms and molybdenum atoms per unit volume]*100

[0071]

[0072] In addition, the method (100) for manufacturing a molybdenum dioxide thin film according to one embodiment may further include an oxidation step of injecting oxygen or a compound containing oxygen to react with the surface of a molybdenum source to control an oxidation state, a heat treatment step of forming a thin film of molybdenum dioxide in a rutile phase from the formed atomic layer, and a purge step of removing unnecessary substances generated during the process of injecting the precursor.

[0073] First precursor refers to the first substrate or surface to be subjected to the process.

[0074] The compound used in the process of introducing oxygen or a compound containing oxygen to control the oxidation state may contain oxygen or be an oxygen molecule itself, and this compound is introduced onto the surface of the first precursor.

[0075] The oxidation process refers to a process of reacting the surface of a first precursor using oxygen or a compound containing oxygen, and changing the oxidation state of the surface of the first precursor through a chemical reaction between the oxygen or a compound containing oxygen and the surface of the first precursor.

[0076] Additionally, a heat treatment process can be performed to form a thin film of molybdenum dioxide in a rutile phase from the formed atomic layer.

[0077] In the rutile phase, rutile is a chemical structure, and in the present invention, it can refer to the phase structure of molybdenum dioxide and tin oxide.

[0078] Molybdenum dioxide (MoO2) is a compound composed of molybdenum and oxygen.

[0079] In the heat treatment process (104), heat treatment is a process of changing the structure or properties of a material at a high temperature, and can form a molybdenum dioxide thin film in a rutile phase from an already formed atomic layer.

[0080] During the reaction process, water molecules interact with the formed atomic layers to activate specific portions, which can be used to control the properties of the compound or improve the properties of semiconductor devices.

[0081] Unnecessary substances generated during the precursor injection process refer to excessive substances or impurities generated when the precursor was injected during the previous process.

[0082] The purge process is a process to remove unnecessary substances. After piling up substances in layers, they can be treated in a specific environment to remove impurities.

[0083] FIG. 2 is a diagram illustrating an atomic layer deposition process cycle (200) for a tin-doped molybdenum dioxide thin film.

[0084] An atomic layer deposition process cycle (200) for a molybdenum dioxide thin film includes a molybdenum source pulse (210) process, an O3 pulse (230) process for oxidation, a Sn source pulse (250) process, and a Sn oxidation source pulse (270) process, and a purge (220, 240, 260) process may be processed between each process.

[0085] In the molybdenum precursor used in the molybdenum source pulse (210) process, the molybdenum temperature is 50°C, and the molybdenum reactant is O3 (210 g / m 3 ), the gas required for the purge process is 99.9999% Ar, and the substrate can be set to the atomic layer deposition process state with SiO2.

[0086] Meanwhile, in the second pulse process, the atomic layer deposition process state can be set with Sn(dmamp)2 as the Sn precursor, Sn temperature of 60°C, H2O as the reactant, and temperature of 300°C.

[0087] In the case of the atomic layer deposition process using a precursor, the self-limiting reaction of the precursor can be performed in 10 s, the self-limiting reaction of O3 (reactant) in 3 s, and the entire process cycle can be performed in 10 s - 10 s - 3 s - 10 s.

[0088] Meanwhile, in the case of the ALD process using the Sn(dmamp)2 precursor, the self-limiting reaction of the precursor can be performed in 6 s, the self-limiting reaction of O3(reactant) in 5 s, and the entire process cycle can be performed in 5 s - 15 s - 6 s - 15 s.

[0089] FIG. 3 is a drawing explaining the composition of a tin-doped molybdenum dioxide thin film obtained through the atomic layer deposition process of FIG. 2 and the structure of a tin-doped molybdenum dioxide thin film formed through subsequent heat treatment, which is a rutile-phase thin film.

[0090] In the case of existing technology, when forming a thin film through an atomic layer deposition process using an organometallic molybdenum source and ozone (O3) reaction gas, it has a composition corresponding to molybdenum trioxide (MoO3) with an orthorhombic structure.

[0091] In order to obtain a molybdenum trioxide thin film composition other than molybdenum trioxide, the present invention uses tin oxide (SnO) in the existing molybdenum trioxide process. x ) can be inserted to secure the composition of molybdenum dioxide, and the structure of the thin film formed through post-heat treatment can be obtained as tin-doped molybdenum dioxide in the rutile phase.

[0092] There is a report that molybdenum dioxide is formed when a molybdenum trioxide process is performed on a substrate, but it is not a single-phase molybdenum dioxide, but a mixed form of molybdenum dioxide and molybdenum trioxide. In addition, molybdenum dioxide cannot be formed on substrates other than TiN due to the formation of molybdenum dioxide by the template effect of the substrate.

[0093] However, in the present invention, it is possible to form a tin-doped molybdenum dioxide thin film on any substrate without the TiN template effect.

[0094] Figure 4 is a drawing explaining the template effect.

[0095] Drawing number 410 is tin dioxide (SnO2), which is structurally similar to molybdenum dioxide of drawing number 420.

[0096] MoO x Tin dioxide crystals in the film induce molybdenum dioxide crystallization through a template effect.

[0097] Figure 5 is a diagram showing self-limiting reactions in different precursors.

[0098] Drawing symbol 510 represents an ALD process using a precursor, in which the self-limiting reaction of the precursor is 10 s, the self-limiting reaction of O3 (reactant) is 3 s, and the entire process cycle represents a self-limiting reaction of 10 s - 10 s - 3 s - 10 s.

[0099] Drawing symbol 520 represents an ALD process using a Sn(dmamp)2 precursor, in which the self-limiting reaction of the precursor is 6 s, the self-limiting reaction of O3(reactant) is 5 s, and the overall process cycle is 5 s - 15 s - 6 s - 15 s.

[0100] Figure 6 shows the reducing power (scavenging effect) of Sn on Mo.

[0101] Drawing symbol 610 represents the formation energy of tin dioxide, which is -2.108 eV / atom, and drawing symbol 620 represents the formation energy of molybdenum dioxide, which is -2.021 eV / atom.

[0102] Figure 7 is a drawing explaining whether TiO2 is formed between the lower layer, TiN, and MoO2.

[0103] Drawing symbol 710 represents a conventional technology in which TiO2 is formed between the lower layer TiN and MoO2, and drawing symbol 720 represents a result formed according to a molybdenum dioxide thin film manufacturing technology according to the present invention in which TiO2 is not formed between the lower layer TiN and MoO2.

[0104] When ALD MoO3 is processed on a TiN substrate, an unwanted TiO2 oxide film may be formed at the TiN / MoO2 interface due to the reaction between TiN and MoO3.

[0105] The leakage current characteristics may deteriorate due to deterioration of electrode characteristics, decrease in capacitance, and increase in roughness caused by surface oxidation, but according to the method for manufacturing a molybdenum dioxide thin film, the problem of forming a TiO2 oxide film between TiN and MoO2 can be solved.

[0106] Figure 8 shows pure Mo-O3ALD on SiO2 and Sn-doped MoO on SiO2. x This is a drawing explaining .

[0107] Drawing symbol 810 represents intensity [arb. units] versus 2-theta [degree] under the condition of Sn 0%.

[0108] Drawing symbol 820 represents intensity [arb. units] versus 2-theta [degree] under the condition of Sn 24%.

[0109] Figure 9 is a drawing explaining crystallization according to the position of the main peak.

[0110] According to Fig. 9, the main peak positions are 26.3° and 35.7°, and the peak at 26.3° is a value between 26.01° of the MoO2 (011) plane and 26.61° of SnO2 (110), and it can be judged that this peak is formed by causing distortion to minimize lattice mismatch while MoO2 and SnO2 crystallize in the same direction.

[0111] The 35.7 ° peak can also be assumed to have occurred due to distortion of the SnO2(101) plane and the MoO2(-202) plane.

[0112] FIG. 10 is a drawing showing a TEM of a thin film obtained through a conventional MoO3ALD process and a drawing showing a TEM of a thin film obtained through a MoO2ALD process developed in the present invention.

[0113] Drawing symbol 1010 represents an XRD of a thin film obtained through a conventional MoO3ALD process, and drawing symbol 1020 represents an XRD of a thin film obtained through a MoO2ALD process developed in the present invention.

[0114] The d-spacing of the MoO2(011) plane is 0.342 nm, and the d-spacing of the SnO2(110) plane is 0.334 nm.

[0115] The d-spacing of the Sn-doped MoO2 formed at this time was 0.338 nm, which confirms that SnO2 and MoO2 were not crystallized separately, but rather in-situ crystallized through lattice distortion.

[0116] Figure 11 is a drawing explaining the composition of a thin film according to the type of oxidizer.

[0117] In Fig. 11, the composition of the thin film deposited at a ratio of 100:3 using a process using H2O and O3 as oxidizing agents for Sn, respectively, can be confirmed.

[0118] It was confirmed that both drawings 1110 and 1120 had ~30% Sn, and no change in the composition of Sn depending on the oxidizing agent could be confirmed.

[0119] However, XRD analysis results showed that Mo4O in the thin film formed when O3 was used as an oxidizing agent 11 You can see that the prize remains fine.

[0120] This means that when the oxidant is strong, the scavenging of Sn is not completely achieved.

[0121] Figure 12 is a diagram showing Sn concentration and resistivity for the MoO3:SnO sub-cycle ratio.

[0122] Drawing symbol 1210 represents Sn concentration [%] versus Sn cycle in Mo-O3ALD 100 cy.

[0123] In drawing code 1210, an experiment was conducted by adding Sn cycles while keeping Mo at a fixed 100 cy. Even when the Mo recipe is conducted at 100 cy, it can be seen that the amount of Mo deposition is affected depending on the number of Sn recipes.

[0124] Additionally, the drawing reference numeral 1220 represents the resistivity [Ωcm] versus Sn cycle per Mo 100cy at Mo- 100cy.

[0125] Drawing number 1220 confirms that the resistivity after heat treatment decreases rapidly as Sn doping progresses, and SEM analysis confirms that the surface morphology improves rapidly according to Sn doping.

[0126] According to the drawings 1210 and 1220, when examining the case where a thin film was obtained by doping ALD MoO3 with tin oxide up to 55%, it can be confirmed that a conductive MoO2 thin film is obtained at the optimal composition.

[0127] For reference, the composition of the thin films deposited at a ratio of 100:3 using a process using H2O and O3 as oxidizing agents for Sn, respectively, was confirmed to contain ~30% Sn for both thin films, and no change in composition depending on the oxidizing agent for Sn could be confirmed.

[0128] However, the XRD analysis results showed that Mo4O in the thin film formed when O3 was used as an oxidizing agent 11 It was confirmed that the prize was still slightly intact.

[0129] This means that when the oxidant is strong, the scavenging of Sn is not completely achieved.

[0130] Figure 13 is a drawing showing that surface roughness decreases as the Sn composition increases.

[0131] According to the present invention, formation of a smooth thin film with excellent thermal stability is possible.

[0132] That is, as seen in Fig. 13, it can be confirmed that the surface roughness decreases as the Sn composition increases.

[0133] Specifically, in drawing code 1300, it can be confirmed that the surface roughness decreases as the Sn composition increases from 0%, 12%, 24%, and 39%.

[0134] Figure 14 is a drawing showing the results of Figure 13 as a graph (1400).

[0135] The graph (1400) of Fig. 14 shows the RMS roughness [nm] according to Sn concentration [%].

[0136] That is, the graph (1400) of Fig. 14 shows that as Sn concentration [%] increases, RMS roughness [nm] decreases.

[0137] Figure 15 is a drawing showing an example of forming high dielectric constant rutile TiO2 on ALD MoO2.

[0138] In particular, drawing symbol 1500 represents a capacitor manufactured based on an atomic layer deposition process.

[0139] Drawing symbol 1510 represents a substrate, and drawing symbol 1520 represents a tin-doped molybdenum dioxide thin film formed on the substrate based on an atomic layer deposition process.

[0140] For example, a tin-doped molybdenum dioxide thin film formed on a substrate is formed by ALD tin oxide (SnO) in an ALD MoO3 process. x ) can be formed by inserting.

[0141] Additionally, a tin-doped molybdenum dioxide thin film formed on a substrate can be formed by controlling the tin ratio up to 55%.

[0142] In addition, drawing symbol 1030 corresponds to a TiO2 layer grown in a rutile structure on a molybdenum dioxide thin film, and drawing symbol 1540 corresponds to an electrode formed on the TiO2 layer, which can be implemented with Pt.

[0143] Figures 16 and 17 show intensity versus 2-theta [degree].

[0144] In the drawing code 1600, it can be confirmed by XRD that TiO2 grows well in a rutile structure on a Sn-doped MoO2 thin film. In addition, according to the drawing codes 1710 to 1730, it can be confirmed that MoO2 appears well when the XRD pick is separated.

[0145] Figure 18 is a drawing (1800) showing the thickness of oxide (EOT, Equivalent Oxide Thickness) compared to the physical thickness.

[0146] According to the graph of drawing number 1800, high dielectric constant rutile TiO2 can be formed on ALD MoO2.

[0147] The dielectric constant of the capacitor fabricated using tin-doped MoO2 was 24%, and the dielectric constant of the tin-doped MoO2 thin film was the highest at 136.45, and the dielectric constant decreased as the doping concentration of tin increased.

[0148] When doped with tin, TiO2 epitaxial growth is achieved very well regardless of the tin doping amount, but it can be confirmed that rutile TiO2 with the highest permittivity is formed at 24%.

[0149] Figure 19 shows the electrical resistivity according to PDA temperature.

[0150] While the above data were based on a Mo subcycle of 100 cy, this data is based on a 300 cy, resulting in some differences in values. However, it can be confirmed that the lowest resistivity was achieved at a heat treatment temperature of 500°C.

[0151] FIG. 20 is a drawing (2000) showing an example of forming high dielectric constant rutile TiO2 on ALD MoO2.

[0152] Compared to drawing number 2010, drawing number 2020 is difficult to form ALD rutile-TiO2 with existing process, so most of it forms anatase-TiO2.

[0153] When ALD MoO3 is formed on a TiN thin film, some MoO2 and MoO3 mixed phases are formed due to the template effect of TiN. However, the present invention has developed a process technology capable of forming an ALD rutile structure MoO2 thin film without such a sub-film effect, and is currently the only known atomic layer deposition-based MoO2 formation method.

[0154] That is, it is original in that the composition and structure are simultaneously controlled by using ALD SnO (monooxide) in forming ALD MoO2, and through this, a method for forming MoO2 based on the atomic layer deposition process that existing technologies could not solve is presented.

[0155]

[0156] Although the embodiments described above have been described with limited drawings, those skilled in the art will recognize that various modifications and variations can be made based on the above description. For example, appropriate results can still be achieved even if the described techniques are performed in a different order than described, and / or components of the described systems, structures, devices, circuits, etc. are combined or combined in a different manner than described, or are replaced or substituted with other components or equivalents.

[0157] Therefore, other implementations, other embodiments, and equivalents to the claims also fall within the scope of the claims described below.

Claims

1. A method for manufacturing a tin-doped molybdenum dioxide (Sn-doped MoO2) thin film based on an atomic layer deposition (ALD) process, The first step is to form molybdenum trioxide (MoO3) by injecting a molybdenum source and ozone (O3) reaction gas onto the substrate surface; Tin oxide (SnO) is formed on the surface of the above-formed molybdenum trioxide (MoO3). x , Tin oxide) to form an atomic layer; and A step of forming a thin film of tin-doped molybdenum dioxide in a rutile phase from the formed atomic layer by repeating the first or second step. A method for manufacturing a tin-doped molybdenum dioxide thin film comprising:

2. In paragraph 1, The step of forming a thin film of the above-mentioned doped molybdenum dioxide is: Step for forming a thin film of molybdenum dioxide doped with tin by 55% or less A method for manufacturing a tin-doped molybdenum dioxide thin film comprising:

3. In paragraph 1, A heat treatment step for forming a thin film of molybdenum dioxide in rutile phase from the above-formed atomic layer. A method for manufacturing a tin-doped molybdenum dioxide thin film further comprising:

4. In paragraph 1, The heat treatment step for forming a thin film of molybdenum dioxide in rutile phase from the above-formed atomic layer is as follows: Heat treatment step at a temperature of 350°C to 600°C A method for manufacturing a tin-doped molybdenum dioxide thin film comprising:

5. In paragraph 1, A method for manufacturing a tin-doped molybdenum dioxide thin film, characterized in that the resistivity of the tin-doped molybdenum dioxide formed from the above atomic layer is reduced compared to the resistivity before tin doping.

6. In paragraph 1, The step of forming a thin film of tin-doped molybdenum dioxide on rutile from the formed atomic layer by repeating the first or second step is as follows: A method for producing a tin-doped molybdenum dioxide thin film, characterized in that a tin-doped molybdenum dioxide thin film is formed regardless of the type of substrate without a template effect.

7. In paragraph 1, The step of forming a thin film of tin-doped molybdenum dioxide on rutile from the formed atomic layer by repeating the first or second step is as follows: A method for producing a tin-doped molybdenum dioxide thin film, characterized in that the surface roughness of the tin-doped molybdenum dioxide thin film decreases as the concentration of tin increases.

8. In paragraph 1, The step of forming a thin film of tin-doped molybdenum dioxide on rutile from the formed atomic layer by repeating the first or second step is as follows: A step for forming a thin film of optimal tin-doped molybdenum dioxide with a tin doping ratio of 24% and a heat treatment temperature of 500°C. A method for manufacturing a tin-doped molybdenum dioxide thin film comprising:

9. Tin-doped molybdenum dioxide (Sn-doped MoO2) thin film electrode formed on a substrate based on an atomic layer deposition (ALD) process; A dielectric layer grown in a rutile structure on the above molybdenum dioxide thin film; and Electrode formed on the above dielectric layer A capacitor using a tin-doped molybdenum dioxide thin film containing .

10. In paragraph 9, The tin-doped molybdenum dioxide thin film formed on the above substrate is Molybdenum source and ozone (O3) reaction gas are injected onto the substrate surface to form molybdenum trioxide (MoO3). Tin oxide (SnO) is formed on the surface of the above-formed molybdenum trioxide (MoO3). x , Tin oxide) to form an atomic layer, A capacitor characterized in that it is formed in the form of a rutile phase from the formed atomic layer by repeating the first or second step.

11. In paragraph 9, The tin-doped molybdenum dioxide thin film formed on the above substrate is Molybdenum trioxide (MoO3) is formed, and tin oxide (SnO) is formed on the surface of the formed molybdenum trioxide (MoO3). x A capacitor characterized by being doped with tin oxide (Tin oxide) to form a tin ratio of up to 55%.

12. In paragraph 9, A capacitor characterized in that the resistivity of the tin-doped molybdenum dioxide formed from the above atomic layer is reduced compared to the resistivity before tin doping.

13. In paragraph 9, A capacitor using a tin-doped molybdenum dioxide thin film, characterized in that a tin-doped molybdenum dioxide thin film is formed regardless of the type of substrate without a template effect.

14. In paragraph 9, A capacitor using a tin-doped molybdenum dioxide thin film, characterized in that the surface roughness of the tin-doped molybdenum dioxide thin film decreases as the concentration of tin increases.

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