KR20160017647A - Preparing method of inorganic thin film containing multiple precursors, and apparatus therefor - Google Patents

Abstract

The present invention relates to a method for manufacturing an inorganic thin film containing multiple precursors and a manufacturing apparatus for the inorganic thin film. Provided is a method for manufacturing an inorganic thin film, which comprises: plasma treating a base material by using a source gas and a reaction gas; and forming an inorganic thin film on the base material as the source gas and the reaction gas react on a surface of the base material by heating the base material at a temperature lower than or equal to a thermal decomposition temperature of the source gas.

Description

TECHNICAL FIELD The present invention relates to a method of manufacturing an inorganic thin film containing multiple precursors,

The present invention relates to a method for producing an inorganic thin film containing multiple precursors and an apparatus for producing the inorganic thin film.

The compound thin film may be a gate dielectric or an intermetallic film such as a semiconductor device and an integrated circuit, a compound semiconductor, a solar cell, a liquid crystal display (LCD) and an organic light emitting diode (OLED) A protective film, and a masking film for preventing a chemical reaction from the surroundings. Therefore, as the size of the semiconductor integrated device becomes smaller and the shape becomes complicated, a technique of coating a uniform thin film having a high step structure is important. Therefore, atomic layer deposition (ALD), which improves the properties of thin films, has been widely used in various fields recently (US Pat. No. 4,058,430).

The ALD utilizes a chemical vapor deposition (ALD) reaction to suppress the gas phase reaction by injecting a precursor and a reactant in a time division manner, and is capable of suppressing a gas phase reaction by using a self-limited reaction Is a process technology for precisely adjusting the thickness of the film. The ALD has excellent step coverage and thickness uniformity, which are characteristic of the self-controlling reaction together with the thickness control of the atomic unit. Therefore, not only a capacitor having a large step difference in structure but also a thin film can be uniformly formed on the inner space of a fiber having a wide surface area and a complicated structure or a surface of a fine particle structure. In addition, since the gas-phase reaction is minimized, the pinhole density is very low, the film density is high, and the deposition temperature can be lowered.

However, ALD is difficult to select suitable precursors and reactants, and the deposition rate is very slow because the thickness of the thin film deposited per cycle is deposited at or below the atomic layer, and the characteristics of the thin film due to excess carbon and hydrogen And the problem is greatly deteriorated at the same time.

On the other hand, deposition of a silicon compound thin film using thermal chemical vapor deposition (TCVD) and plasma enhanced chemical vapor deposition (PECVD) is very fast compared with ALD. However, since there are many pinholes in the thin film and problems such as by-products and particle generation may occur, it is difficult to apply the thin film to a substrate such as a plastic film because the thin film is generated mainly at a high temperature.

The present invention provides a method for producing an inorganic thin film containing multiple precursors and an apparatus for producing the inorganic thin film.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: alternately subjecting a substrate to plasma treatment using a source gas and a reactive gas; and forming a thin film of an inorganic thin film on the substrate by reacting the source gas and the reactive gas on the surface of the substrate Wherein the plasma processing of the source gas and the reactive gas is performed in a respective independent plasma module and the source gas is a precursor containing a metal selected from the group consisting of silicon, zirconium, titanium, and combinations thereof. And an inert gas. The present invention also provides a method for producing an inorganic thin film containing multiple precursors.

A second aspect of the present invention is a substrate processing apparatus including a substrate loading unit to which a substrate is loaded, a substrate transporting unit coupled to the substrate loading unit to alternately move the substrate, a substrate heating unit provided at a lower end of the substrate transporting unit to heat the substrate, Wherein the inorganic thin film deposition unit includes a plurality of source plasma modules and a plurality of reaction plasma modules, and wherein the substrate transport unit is configured to alternate the source plasma module and the reaction plasma module And an inorganic thin film is deposited on the substrate by moving the organic thin film.

According to one embodiment of the present invention, the source plasma and the reaction plasma are separately injected into the substrate, and by using the scanning type CVD, excellent characteristics such as low hydrogen content, low pinhole density, and high film density at a temperature of about 400 ° C or lower , And the inorganic thin film may be applied to an encapsulation film or a barrier film. In addition, in one embodiment of the invention, the deposition rate of the inorganic thin film has a high deposition rate of about 5 A / s to about 10 A / s, so that it is excellent in mass productivity. In addition, a uniform thin film can be produced with few particles during the process.

Further, continuous deposition of multi-component metal-oxide thin films and metal-nitride thin films and / or alternating deposition is possible.

Meanwhile, the high-speed deposition apparatus for an inorganic thin film according to an embodiment of the present invention is advantageous in that the apparatus is simple in configuration, is easy to deform, has a wide application range, and can be applied to a roll-to-roll and large-film deposition facility.

1 is a schematic view showing an apparatus for producing an inorganic thin film according to an embodiment of the present invention.
2 is a schematic view showing an apparatus for manufacturing an inorganic thin film including a plurality of plasma modules according to an embodiment of the present invention.
3 is a schematic view showing an apparatus for producing an inorganic thin film according to an embodiment of the present invention.
4 is a schematic view showing an apparatus for producing an inorganic thin film according to an embodiment of the present invention.
5 is a schematic view showing an apparatus for producing an inorganic thin film according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.

According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: alternately subjecting a substrate to plasma treatment using a source gas and a reactive gas; and forming a thin film of an inorganic thin film on the substrate by reacting the source gas and the reactive gas on the surface of the substrate Wherein the plasma processing of the source gas and the reactive gas is performed in a respective independent plasma module and the source gas is a precursor containing a metal selected from the group consisting of silicon, zirconium, titanium, and combinations thereof. And an inert gas. The present invention also provides a method for producing an inorganic thin film containing multiple precursors.

In one embodiment of the present invention, since the reaction of the source gas and the reaction gas occurs on the surface of the substrate, not the gas phase, by performing the plasma treatment of the source gas and the reactive gas in independent plasma modules, And the source gas and the reactive gas are not directly reacted with each other, thereby reducing damage caused by byproducts generated in the reaction and UV. In addition, by performing the plasma treatment of the source gas and the reactive gas simultaneously in independent plasma modules, the deposition rate of the inorganic thin film according to one embodiment of the present invention can be improved.

In addition, the power used in the plasma treatment may be lowered to reduce impurities and / or electrode damage at high power, but may not be limited thereto.

According to one embodiment of the present invention, the inert gas may include, but is not limited to, selected from the group consisting of Ar, He, Ne, and combinations thereof.

According to one embodiment of the present invention, the reaction gas may include, but is not limited to, those selected from the group consisting of N ₂ , H ₂ , O ₂ , N ₂ O, NH ₃ , .

According to one embodiment of the invention, the substrate may additionally include, but is not limited to, heating the substrate at a temperature of about 400 ° C or less. In one embodiment of the invention, the substrate may be heated during the inorganic thin film manufacturing process and the substrate may be heated to a temperature below the pyrolysis temperature of the silicon precursor, zirconium precursor, or titanium precursor, The chemical reaction of the silicon precursor, the zirconium precursor, or the titanium precursor and the reaction gas may be induced. For example, the substrate may be, but not limited to, heating at a temperature of about 400 ° C or less, about 300 ° C or less, about 200 ° C or less, or about 100 ° C or less. In one embodiment of the present invention, when the inorganic thin film is used as a sealing film, the substrate may be heated at about 100 ° C or less. When the inorganic thin film is used as a barrier film, But may be performed in a temperature range of from about 100 DEG C to about 400 DEG C, but is not limited thereto.

According to one embodiment of the present invention, alternating plasma treatment of the substrate using the source gas and the reactive gas may be repeated at least once, but the present invention is not limited thereto. For example, alternately performing plasma processing using the source gas and the reactive gas may be performed by a first plasma process, a second plasma process using the source gas and the reaction gas to an inorganic thin film formed on the substrate through the first plasma process The alternating plasma treatment may be referred to as a second plasma treatment. The second plasma treatment may include performing n-th plasma treatment (n is an integer of 1 or more) by repeating it n times (where n is an integer of 1 or more) But may not be limited.

In one embodiment of the present invention, the inorganic thin film having an inorganic / inorganic structure can be formed on the substrate by repeating the plasma treatment at least once or more. For example, the second inorganic thin film can be formed on the first inorganic thin film by performing the second plasma treatment on the first inorganic thin film formed on the substrate through the first plasma treatment, (N is an integer of 1 or more) repeatedly to form an n-th inorganic thin film (n is an integer of 1 or more) on the substrate.

According to one embodiment of the present invention, the plasma processing of the source gas and the reactive gas may be performed simultaneously or alternately in independent plasma modules, but the present invention is not limited thereto. For example, when the plasma processing of the source gas and the reactive gas is performed simultaneously from independent plasma modules, the inorganic thin films are formed in a mixed structure on the substrate, and for example, the source gas and the reactive gas Are formed in a structure in which an inorganic thin film is laminated on a substrate when the plasma processing of the plasma processing is performed alternately from each independent plasma module.

In one embodiment of the present invention, the inorganic thin film having the inorganic / inorganic structure formed through the n-th plasma treatment (n is an integer of 1 or more) on the substrate shows a laminated structure and / or a mixed structure. For example, when the inorganic thin film is formed on the substrate without mixing the layers, excellent barrier properties and excellent flexibility can be achieved.

In one embodiment of the invention, the first plasma treatment, the second plasma treatment, , And the n-th plasma process (where n is an integer of 1 or more), the source gas and the reactive gas used in the plasma treatment may be the same or different.

According to an embodiment of the present invention, the thickness of the inorganic thin film may be about 300 Å to about 2,000 Å, but the present invention is not limited thereto. For example, the thickness of the inorganic thin film may range from about 300 A to about 2,000 A, from about 300 A to about 1,800 A, from about 300 A to about 1,600 A, from about 300 A to about 1,400 A, from about 300 A to about 1,200 A, From about 300 A to about 1000 A, from about 300 A to about 800 A, from about 300 A to about 600 A, or from about 300 A to about 400 A.

According to one embodiment of the present invention, the inorganic thin film may be formed using a chemical vapor deposition method or an atomic layer deposition method, but the present invention is not limited thereto.

A second aspect of the present invention is a substrate processing apparatus including a substrate loading unit to which a substrate is loaded, a substrate transporting unit coupled to the substrate loading unit to alternately move the substrate, a substrate heating unit provided at a lower end of the substrate transporting unit to heat the substrate, Wherein the inorganic thin film deposition unit includes a plurality of source plasma modules and a plurality of reaction plasma modules, and wherein the substrate transport unit is configured to alternate the source plasma module and the reaction plasma module And an inorganic thin film is deposited on the substrate by moving the organic thin film.

1 is a schematic view showing an apparatus for producing an inorganic thin film according to an embodiment of the present invention.

Referring to FIG. 1, an apparatus for manufacturing an inorganic thin film according to an embodiment of the present invention includes a substrate loading unit 100, a substrate transport unit 200, a substrate heating unit 300, and an inorganic thin film deposition unit 400.

First, the substrate 10 is loaded onto the substrate loading unit 100. The substrate 10 can be, but is not limited to, a substrate commonly used for semiconductor devices, including those selected from the group consisting of quartz, glass, silicon, polymers, and combinations thereof.

In one embodiment of the present invention, the substrate transport unit 200 is coupled to the substrate loading unit 100 to move the substrate 10. At this time, the direction of movement of the substrate 10 may be alternating with a linear or non-linear path, but may not be limited thereto.

The inorganic thin film deposition unit 400 includes a source plasma module 410 and a reaction plasma module 410. The inorganic thin film deposition unit 400 includes a source plasma module 410 and a reaction plasma module 420, 420). The source plasma module 410 and the reaction plasma module 420 may additionally include electrodes for generating plasma, but the present invention is not limited thereto.

In one embodiment, the source plasma module 410 and the reaction plasma module 420 may include a source gas and a reactive gas, respectively, and the source gas and the reactive gas may be converted into a plasma state for a short period of time 10), and may be exhausted, but the present invention is not limited thereto.

According to one embodiment of the invention, the source plasma module may be plasma treated with a precursor containing a metal selected from the group consisting of silicon, zirconium, titanium, and combinations thereof, and an inert gas, .

According to one embodiment of the present invention, the inert gas may include, but is not limited to, selected from the group consisting of Ar, He, Ne, and combinations thereof.

According to one embodiment of the present invention, in the reaction plasma module, a reaction gas selected from the group consisting of N ₂ , H ₂ , O ₂ , N ₂ O, NH ₃ , and combinations thereof may be plasma treated, But may not be limited.

In one embodiment of the present invention, when source gas and reactive gas are supplied to the substrate 10 by the source plasma module 410 and the reaction plasma module 420, respectively, the source gas and the reactive gas The inorganic thin film may be formed on the substrate 10 by physical or chemical reaction at the surface of the substrate 10, but the present invention is not limited thereto. For example, the temperature of the substrate 10 may be controlled by the substrate heating unit 300 to induce a chemical reaction between the source gas and the reactive gas on the surface of the substrate 10.

In one embodiment of the present invention, when the plasma processing is performed from the inorganic thin film deposition unit 400, the plasma processing may be performed simultaneously or alternately from the source plasma module 410 and the reaction plasma module 420 However, the present invention is not limited thereto. For example, when the source plasma treatment and the reaction plasma treatment are performed simultaneously from independent reactors, the inorganic thin films are formed in a mixed state with each other on the substrate. For example, the source plasma treatment and the reaction plasma treatment Are alternately formed from independent reactors, they are formed in a structure in which an inorganic thin film is laminated on a substrate.

According to one embodiment of the present invention, the substrate heating unit 300 adjusts the temperature of the substrate 10 so that when the inorganic thin film is deposited on the surface of the substrate 10, Keep it below pyrolysis temperature. The lower the substrate temperature than the thermal decomposition temperature of the source gas, the more the source gas is adsorbed to the substrate. For example, the source gas has a pyrolysis temperature of about 100 ° C to about 700 ° C. However, in the case of thin film deposition for semiconductor devices, a temperature of about 400 DEG C or less is preferable in order to reduce the impurity diffusion in the substrate. For example, the temperature of the substrate 10 controlled by the substrate heating unit 300 may be about 400 ° C. or less, about 300 ° C. or less, about 200 ° C., or about 100 ° C. or less, have.

In an embodiment of the present invention, when an inorganic thin film is manufactured using the apparatus of FIG. 1, the inorganic thin film is formed with an inorganic thin film of about 500 ANGSTROM to about 2,000 ANGSTROM on the substrate in accordance with the source gas and the reactive gas . For example, as shown in FIG. 1, the inorganic thin film deposition unit 400 may include a source plasma module 410 and a reaction plasma module 420, respectively. The source plasma module 410 may include a source SiO ₂ having a thickness of about 500 ANGSTROM to about 2,000 ANGSTROM is formed on the substrate 10 when a silicon precursor is injected as a gas and oxygen is injected as a reactive gas into the reaction plasma module 420 to perform a plasma treatment at the same time, An inorganic thin film is formed.

2, a source plasma module 410, a first reaction plasma module 421, and a second reaction plasma module 422 may be used as the inorganic thin film deposition unit 400. In this embodiment, When the plasma processing is simultaneously performed from the source plasma module 410, the first reaction plasma module 421 and the second reaction plasma module 422 using an apparatus including the plasma processing apparatus, . For example, a silicon precursor is injected as a source into the source plasma module 410, oxygen is injected into the first reaction plasma module 421 as a reaction gas, and the reaction gas The inorganic thin film formed by mixing SiO ₂ and SiN is formed on the substrate.

3, as the inorganic thin film deposition unit 400, a first reaction plasma module 421, a first source plasma module 411, a second source plasma module 412 ), And the second reaction plasma module 422, the inorganic thin film is formed on the substrate without mixing the layers when the plasma treatment is simultaneously performed. For example, nitrogen may be injected into the first reaction plasma module 421 as a reactive gas, a silicon precursor may be injected into the first source plasma module 411 as a source gas, When a zirconium precursor is injected as a gas and nitrogen is injected into the second reaction plasma module 422 as a reaction gas to simultaneously perform the plasma treatment, an inorganic thin film mixed with SiN and ZrN is formed on the substrate.

4, the inorganic thin film deposition unit 400 includes a first reaction plasma module 421, a first source plasma module 411, and a second source plasma module (not shown) 412 on the substrate 10 using the first reaction plasma module 421 and the first source plasma module 411 using an apparatus including a first reaction plasma module 422 and a second reaction plasma module 422, When the second plasma processing is performed alternately using the second source plasma module 412 and the second reaction plasma module 422, an inorganic thin film is formed on the substrate 10 do. For example, after nitrogen is injected into the first reaction plasma module 421 as a reaction gas and a silicon precursor is injected into the first source plasma module 411 as a source gas to perform a first plasma treatment, The second plasma process is performed by injecting a silicon precursor as a source gas into the second source plasma module 412 and oxygen as a reaction gas to the second reaction plasma module 422 and alternately performing the second plasma process, A thin film and a SiO ₂ thin film are stacked and formed. For example, after nitrogen is injected into the first reaction plasma module 421 as a reaction gas and a silicon precursor is injected into the first source plasma module 411 as a source gas to perform a first plasma treatment, A second plasma process is performed by injecting a zirconium precursor as a source gas into the second source plasma module 412 and oxygen as a reaction gas to the second reaction plasma module 422 and alternately performing the second plasma process, Thin film and a ZrO ₂ thin film are stacked and formed.

5 is a schematic view showing an apparatus for manufacturing an inorganic thin film including a plurality of plasma modules according to an embodiment of the present invention.

5, the inorganic thin film deposition unit 400 includes a plurality of source plasma modules 410 and a plurality of reaction plasma modules 420, But may not be limited thereto.

In one embodiment of the present invention, the inorganic thin film may exhibit a nano-laminated structure and / or a mixed structure depending on the configuration of the source plasma module 410 and the reaction plasma module 420.

The manufacturing apparatus for high-speed deposition of an inorganic thin film according to the present invention can be applied not only to the manufacturing apparatus shown in Figs. 1 to 5 but also to a modification and / or a mixture thereof. It is applicable to the deposition equipment.

Further, although not shown, in one embodiment of the present invention, the apparatus for producing a multi-layered inorganic thin film may include, but is not limited to, a controller. The control unit may be coupled to the substrate loading unit, the substrate transport unit, the substrate heating unit, and the thin film deposition unit of the multi-layer inorganic thin film production apparatus to control conditions required for manufacturing the inorganic thin film. For example, the controller may control the injection time, intensity, wavelength, and duty cycle of the reaction plasma and the source plasma during the deposition of the inorganic thin film, but the present invention is not limited thereto.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

10: substrate
100: substrate loading unit
200:
300: substrate heating section
400: inorganic thin film deposition unit
410: source plasma module
411: first source plasma module
412: second source plasma module
420: Reaction Plasma Module
421: first reaction plasma module
422: second reaction plasma module

Claims (6)

Subjecting the substrate to plasma treatment using a source gas and a reactive gas; And
And heating the substrate to a temperature not higher than the thermal decomposition temperature of the source gas so that the source gas and the reactive gas react on the surface of the substrate to form an inorganic thin film on the substrate
/ RTI >
Wherein the plasma processing of the source gas and the reactive gas is performed in a plurality of independent source plasma modules and a plurality of reaction plasma modules,
Wherein the source gas comprises an inert gas and a precursor containing two or more metals selected from the group consisting of silicon, zirconium, titanium, and combinations thereof,
Wherein the inorganic thin film is formed on the substrate by plasma treatment of the source gas and the reactive gas, and the inorganic thin film is formed by mixing or laminating the substrate on the substrate simultaneously or alternately at least once.
A method for producing an inorganic thin film.
The method according to claim 1,
Wherein the inert gas is selected from the group consisting of Ar, He, Ne, and combinations thereof.
The method according to claim 1,
Wherein the reaction gas is selected from the group consisting of N ₂ , H ₂ , O ₂ , N ₂ O, NH ₃ , and combinations thereof.
The method according to claim 1,
And heating the substrate at a temperature of 400 DEG C or less.
The method according to claim 1,
Wherein the inorganic thin film has a thickness of 300 ANGSTROM to 2,000 ANGSTROM.
The method according to claim 1,
Wherein the inorganic thin film is formed using a chemical vapor deposition method or an atomic layer deposition method.

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