KR101076172B1 - Vapor Deposition Reactor - Google Patents

Abstract

The vapor deposition reactor includes: a first injection unit for injecting a first material into a substrate; And a reaction module positioned in the first injection unit and including one or more second injection units for injecting a second material into the substrate. The reaction module may have a structure in which the substrate passes through the reaction module in a relative movement with the substrate. The vapor deposition reactor has an advantage of injecting a plurality of materials into the substrate without exposing the substrate passing through the reaction module to the atmosphere in the chamber.

Atomic layer, deposition, reactor, ALD, chamber, precursor

Description

Vapor Deposition Reactor

Embodiments are directed to a vapor deposition reactor.

Examples of semiconductor materials include silicon-based semiconductors such as Si and SiGe, metal oxide semiconductors such as ZnO, III-V-based compound semiconductors such as GaAs, GaP, GaN, AlGaAs, and InP, or II- such as CdSe, CdTe, ZnS, and CdHgTe. VI-based compound semiconductors and the like. These materials are used as substrate materials, and metal films, insulating films, and the like are formed on the substrate to fabricate semiconductor devices through photolithography, etching, cleaning, thin film deposition and the like.

Metal-Oxide-Semiconductor Field Effect Transistors (MOSFETs), which are widely used for high integration, form an insulating film on a semiconductor substrate and use it as a gate insulating film of a transistor. Allow voltage or current to flow. At this time, the reaction between the substrate and the metal film or the insulating film is very important, and even the slight reactions of the semiconductor device characteristics of the semiconductor control is required precisely.

The deposition method for this purpose is also gradually changing from atomic CVD (Atomic Layer Deposition) to CVD such as low pressure chemical vapor deposition (LPCVD) obtained in a furnace (furnace) apparatus. ALD consists of four steps: source precursor injection, physical adsorption layer removal, reactant precursor injection and physical adsorption layer removal.

1 is a flowchart illustrating an atomic layer deposition method according to the prior art.

Referring to FIG. 1, in the atomic layer deposition method, a step of loading a substrate (S11), a step of injecting a precursor precursor by passing the substrate through a precursor precursor supply module (S12), and a purge / pumping module of the substrate Removing the physical adsorption layer of the raw material precursor by passing through the step (S13), passing the substrate through the reaction precursor supply module to inject the reaction precursor (S14), and passing the substrate through the purge / pumping module to physically adsorb the reaction precursor. It may include the step (S15) of removing the layer.

The above steps may be performed repeatedly until the final thickness of the desired atomic layer is obtained (S16). At this time, the raw material precursor, the purge gas (purge gas), the reaction precursor, the purge gas, etc. are sequentially supplied to the substrate using an expensive atomic layer deposition method dedicated valve to implement each step.

Since the raw material precursor is deposited on the deposited semiconductor substrate by HF or other chemicals, the raw material precursor is directly contacted with the semiconductor substrate. While the raw material precursor is first adsorbed to the substrate, interdiffusion may occur or an unwanted interface may be formed on the surface of the semiconductor substrate by reaction of the substrate and the raw material precursor.

If the design rule of the semiconductor device is large enough, such a phenomenon may be insignificant, and the effect on the characteristics of the semiconductor device may be small, but the device may be gradually miniaturized to have a design rule of about 32 nm or less, or a nano device. In quantum devices, the reaction at the interface, the formation of the unwanted interface or the reaction can have a serious effect.

Embodiments of the present invention provide a vapor deposition reactor capable of injecting a plurality of different materials by each injection unit into a substrate passing through the reaction module by configuring the reaction module of the vapor deposition reactor in which one injection unit is positioned. Can be provided.

According to one embodiment, a vapor deposition reactor includes: a first injection unit for injecting a first material into a substrate; And a reaction module positioned in the first injection unit and including one or more second injection units for injecting a second material into the substrate. The reaction module may have a structure in which the substrate passes through the reaction module in a relative movement with the substrate.

Since the vapor deposition reactor according to the embodiments is configured such that at least one second injection unit is positioned in the first injection unit of the reaction module, a plurality of different materials may be injected into the substrate by the first injection unit and the second injection unit, respectively. Can be. Accordingly, a thin film may be formed by injecting a raw material precursor or a reaction precursor into the substrate without exposing the substrate to an atmosphere in the chamber. The vapor deposition reactor may be used for atomic layer deposition (ALD).

Hereinafter, some embodiments of the present invention will be described in detail with reference to the accompanying drawings.

2 is a schematic perspective view of a vapor deposition reactor according to one embodiment.

Referring to FIG. 2, the vapor deposition reactor may include one or more reaction modules 20. The one or more reaction modules 20 may be located in the chamber 10, and one or more substrates 1 may be loaded in the support 100 in the chamber 10. The chamber 10 may be in a vacuum state. For example, if it is necessary to lower the base vacuum level of the chamber 1 to 10 ⁻³ Torr or less in order to form a thin film affected by residual oxygen, such as a metal film, the turbo may be applied to the chamber 10. A vacuum pump such as a turbo-molecular pump (TMP) may be provided. Alternatively, the chamber 10 may be filled with a predetermined material.

Since the temperature of the substrate 1 and the temperature of the atmosphere of the chamber 10 also influence the reaction, the chamber 10 may be provided with a heating device (not shown) for controlling the temperature. In the case where the heating device of the substrate 1 is located below the chamber 10 to indirectly heat the substrate 1, the space used for the deposition and the space of the heating device are located in the chamber 10, the support part 100, or the like. It is separated by. In this case, the heating device may be purged by injecting an inert gas such as Ar so that the material required for deposition is not mixed into the heating device. The pressure of the injected purge gas can be adjusted so as not to be lower than the pressure in the deposition space and not to degrade the deposition characteristics.

Although a cylindrical chamber 10 is shown in FIG. 2, this is exemplary and the chamber 10 may have any shape that can accommodate the substrate 1 and the reaction module 20. The shape of the substrate 1 is also not limited to the disk shape shown in FIG. 2 and a substrate having any shape may be used.

One or more reaction modules 20 may be disposed in a fixed position within chamber 10. On the other hand, the support part 100 on which the substrate 1 is mounted may rotate. At this time, the rotational speed of the support 100 may be constant, or may be programmed by a computer to have a different speed depending on the position. The support 100 may rotate to allow the substrate 1 to pass through the lower portion of the reaction module 20. In contrast, in another embodiment, relative movement of the substrate 1 and the reaction module 20 may be generated by fixing the position of the substrate 1 and rotating the reaction module 20.

Although the vapor deposition reactor is a rotary type, the substrate 1 is moved relative to the reaction module 20 by the rotational movement, but the relative relationship between the substrate 1 and the reaction module 20 in the vapor deposition reactor according to another embodiment. The movement may be a linear movement or a reciprocating movement.

While the substrate 1 passes under the reaction module 20, the substrate 1 and the reaction module 20 may be spaced apart from each other to maintain a non-contact state. The substrate 1 passing through the reaction module 20 may be exposed to a material injected from the reaction module 20, so that an adsorption layer may be formed on the substrate 1.

The materials injected in each reaction module 20 may be the same as or different from each other. For example, a substrate is passed through two reaction modules 20 by injecting reactant precursors using one reaction module 20 and a source precursor using another reaction module 20. You may form an atomic layer thin film on (1). This will be described later in detail with reference to FIGS. 3A and 3B.

In one embodiment, the reaction module 20 may include a plasma, ultra-high frequency or ultraviolet generator according to the type of thin film to be formed. Furthermore, a thin film may be formed by using two or more of the aforementioned energy sources in one process or by using the aforementioned energy sources step by step. This will also be described later in detail.

3A is a cross-sectional view of a vapor deposition reactor according to one embodiment, and FIG. 3B is a partial enlarged view of a region where the substrate 1 and the reaction module 20 are adjacent in FIG. 3A.

Referring to FIGS. 3A and 3B, the substrate 1 may be fixed by a susceptor 101 of the support part 100 and may move from the left side to the right side of the drawing. That is, the substrate 1 passes through the lower part of the reaction module 20 from left to right. The substrate 1 and the reaction module 20 may be spaced apart from each other to maintain a non-contact state. For example, the distance between the substrate 1 and the reaction module 20 may be about 1 mm to several mm. Before moving to the lower portion of the reaction module 20, impurities or adsorbates due to the atmosphere in the chamber 10 may be formed on the surface of the substrate 1.

In one embodiment, the chamber 10 may include a channel 115 in an area adjacent to the substrate 1. In this case, the remaining region in the chamber 10 except for the channel 115 may be filled with the filler 110. The filler 110 may be made of the same material as the outer wall of the chamber 10. In the case of filling the material in the chamber 10, the use of such a configuration can reduce the amount of the material to be filled, which is an economic advantage.

The reaction module 20 may include a first injection unit 201 and a second injection unit 202 positioned in the first injection unit 201. In addition, the first and second injection units 201 and 202 may be located in the exhaust unit 203. The size of the reaction module 20 and the size of each of the first injection unit 201, the second injection unit 202, and the exhaust unit 203 may be appropriately determined based on the material to be injected or the type of thin film to be formed. .

The exhaust part 203 and the first injection part 201 may be spaced apart from each other in a direction perpendicular to the moving direction of the substrate 1. In addition, the first injection unit 201 and the second injection unit 202 may also be spaced apart at a predetermined interval Z in a direction perpendicular to the moving direction of the substrate 1. In addition, the first and second injection parts 201 and 202 may be spaced apart at predetermined intervals X and Y, respectively, in the moving direction of the substrate 1 and the reverse direction thereof. The above-described gaps H, X, Y, and Z may be appropriately determined based on the material to be injected or the type of thin film to be formed.

When a part or the entire area of the substrate 1 moved from the left side is located under the exhaust part 203 of the reaction module 20, the exhaust part 203 causes impurities or adsorbates in the corresponding area to enter the chamber 10. Can be discharged outside. When the substrate 1 is moved to the right side and the corresponding region is located below the first injection unit 201, the first injection unit 201 may inject the first material into the substrate 1.

For example, the first material may be a purge gas. By injecting the purge gas into the substrate 1, molecules physically adsorbed on the substrate 1 can be removed. As a result, only the chemisorption layer generated in the preceding process remains on the substrate 1, or in the absence of the preceding process, the adsorption layer may be in a state. Inert gas may be used as the purge gas. For example, the purge gas is N ₂ Gas, Ar gas, He gas, or other suitable materials, and may include two or more combinations of the foregoing materials. The first material may include a raw material precursor or a reaction precursor for forming an atomic layer.

When the substrate 1 is moved to the right and a part or the entire area is positioned below the second injection portion 202, the second injection portion 202 may inject the second material into the substrate 1. The second material may be a material for forming a thin film on the substrate 1. For example, the second material may include a raw material precursor or a reaction precursor for forming an atomic layer.

In this case, as the reaction precursor, a material for obtaining a metal, an oxide, a nitride, a carbide, a semiconductor material, or the like from a chemical raw material may be used. For example, the reaction precursors are H ₂ O, H ₂ O ₂ , O ₂ , N ₂ O, O ₃ , O * radicals, NH ₃ , NH ₂ —NH ₂ , N ₂ , N * radicals, CH ₄ , C ₂ H ₆ Organic carbon compounds, H ₂ , H * radicals, or other suitable materials, and the like, and combinations of two or more of the foregoing materials.

In addition, as the raw material precursor, a material capable of forming a thin film on the substrate 1 by reacting and / or replacing with the reaction precursor may be used. The type of raw material precursor may vary according to the type of thin film to be formed. For example, in the case of a semiconductor thin film, the raw material precursor may be a Group IV compound, a III-V compound, or a II-VI compound. In the case of the metal thin film, the raw material precursor is Ni-based compound, Co-based compound, Al-based compound, Ti-based compound, Hf-based compound, Zr-based compound, Ta-based compound, Mo-based compound, W-based compound, or a compound of these materials and Si It may be. Furthermore, in the case of the dielectric or conductive dielectric thin film, the raw material precursor may be a Ni-based compound, a Zn-based compound, a Cu-based compound, a Co-based compound, an Al-based compound, a Si-based compound, an Hf-based compound, a Ti-based compound, a Zr-based compound, or a Ta-based compound. Compound and the like. The raw material precursor may comprise a combination of two or more of the substances listed above.

Si-based compounds that can be used as the raw material precursors include SiH ₄ or SiH ₂ Cl ₂ . Examples of the Ti-based compound include TiCl ₄ . Al-based compounds include trimethyl aluminum (TMA). Examples of Hf-based compounds include tetrakis-ethylmethylaminohafnium (TEMAHf). Examples of Zr-based compounds include tetrakis-ethylmethylaminozirconium (TEMAZr). The type of raw material precursor is not limited to the above-described materials, and various materials may be used in addition to those listed according to the type of thin film as the final product.

On the other hand, the reaction precursor may be in the form of a plasma (plasma) of the above-described materials, or may be applied with light such as ultraviolet rays. Even if plasma, radicals, or photons are applied to decompose the reaction precursors, the by-products are not likely to remain in the resulting thin film and do not deteriorate or deteriorate the thin film properties. When the reaction precursor activated by these energies is used, sufficient adsorption molecules can be obtained even when a Si-based compound or TiCl ₄ or the like, which is not easily formed in a thin film, is used as a precursor. Therefore, the deposition rate of the thin film can be increased, and the surface treatment or the interface treatment of the substrate 1 can be facilitated.

The first and second injection parts 201 and 202 described above may be injectors in the form of rectangular showerheads. Alternatively, when the support 100 is rotated, since the angular velocities of the inside and the outside of the substrate 1 are different, the first and second injection portions 201 and 202 may have a pi proportional to the angular velocity to improve the uniformity of the thin film. It may also be an injector in the form of a (pie) showerhead.

When the substrate 1 moves further to the right and the corresponding region passes through the second injection portion 202, the substrate 1 is again positioned under the first injection portion 201. The first injection unit 201 may inject a first material such as a purge gas into the substrate 1. The physical adsorption layer and the chemical adsorption layer of the second material are positioned in the region of the substrate 1 passing through the second injection unit 202, and the physical adsorption layer is formed by the purge gas injected by the first injection unit 201. It can be separated from the substrate 1.

When the substrate 1 moves further to the right, the corresponding region is located under the exhaust part 203, so that the physical adsorption layer of the purge gas and the second material may be pumped out of the chamber 10 and removed. As a result, only the chemisorption layer of the second material remains on the surface of the substrate 1 passing through the reaction module 20.

That is, while the substrate 1 passes through one reaction module 20, three kinds of first material injection-> second material (reactive precursor or raw material precursor) injection-> first material injection are injected onto the substrate 1. It goes through the steps. A pumping step by the exhaust part 203 may be added before or after the three steps. As the position of the second injection unit 202 is changed (or spaced apart from the first injection unit 201), the first injection unit 201 after the substrate 1 passes through the second injection unit 202. ) And the time passing through the interval Y between the second injection portion 202 is changed, the injection time of the first material is changed. Thus it is advantageous to optimize the amount or time of purge when using precursors with different adsorption properties. As a result, only the chemisorption layer of the reaction precursor or raw material precursor may remain on the substrate 1 passing through the reaction module 20.

In one embodiment, when the interval Y between the first injection unit 201 and the second injection unit 202 is shortened, the reaction precursor or the precursor precursor is insufficient because the time for purging the reaction precursor or the precursor precursor is insufficient. A portion of the physical adsorption layer may be left on the substrate 1. In this case, the deposition rate of the thin film may be improved compared to the pure atomic layer deposition due to the remaining physical adsorption layer.

The thin film may be formed on the substrate 1 by passing the substrate 1 on which the chemical adsorption layer of the reaction precursor or the precursor precursor is formed, through another reaction module 20. For example, the substrate 1 on which the chemisorption layer of the reaction precursor is formed by passing through one reaction module 20 may be passed through another reaction module 20 into which the raw material precursor is injected. As a result, an atomic layer thin film can be formed on the substrate 1 by substitution and / or reaction of the reaction precursor and the raw material precursor. Alternatively, the atomic layer thin film may be formed by first forming the chemical adsorption layer of the raw material precursor on the substrate 1 by one reaction module 20 and injecting the reaction precursor by the other reaction module 20. .

3C and 3D are cross-sectional views of a reaction module in a vapor deposition reactor according to other embodiments.

Referring to FIG. 3C, the separation distance X (see FIG. 3B) between the first injection unit 201 and the second injection unit 202 along the reverse direction of the movement direction of the substrate 1 may be zero. That is, the second injection portion 201 may be in contact with either of the inner walls of the first injection portion 201. Meanwhile, referring to FIG. 3D, the second injection unit 202 may be in contact with the wall opposite to the case of FIG. 3C among the inner walls of the first injection unit 201.

As illustrated in FIGS. 3C and 3D, various types of deposition may be performed by adjusting the spacing X, Y, and Z in each direction between the first and second injection portions 201 and 202. have.

3E is a cross-sectional view of a vapor deposition reactor according to another embodiment. In the above embodiment, after the purge gas is injected from the sidewall of the first injection unit 201, a portion of the precursor adsorbed on the substrate 1 may be detached from the substrate 1 while passing through the substrate 1. The desorbed precursor may be exhausted to the exhaust unit 203. The second injection unit 202 may be in contact with an upper portion inside the first injection unit 201. Since the purge gas is injected from the sidewall of the first injection unit 201, the purge gas is injected in a direction opposite to the moving direction of the substrate 1 and then exhausted to the exhaust unit 203. On the other hand, in another embodiment, purge gas may be injected from the sidewall opposite to that shown in FIG. 3E in the first injection unit 201.

Operation of the vapor deposition reactor illustrated in FIGS. 3C to 3E may be easily understood by those skilled in the art from the foregoing description with reference to FIGS. 3A and 3B, and thus a detailed description thereof will be omitted.

4A is a side cross-sectional view of a first injection portion 201 in a vapor deposition reactor in accordance with one embodiment. As shown, the first inlet 201 may include a channel 2 in the form of a pipe through which the first material is injected and carried. The first material carried through the channel 2 can be injected into the underlying substrate through one or more holes 3 formed in the channel 2. The size of each hole 3 may be constant or may be different from each other. 4A exemplarily illustrates a configuration of the first injection unit 201, the configuration of the second injection unit 202 may also be the same.

4B is a bottom view of a reaction module of a vapor deposition reactor according to one embodiment. As shown, the second injection unit 202 may be located in the first injection unit 201 to be spaced apart from the first injection unit 201. The second material may be injected through one or more holes 3 of the second injection portion 202. In the bottom view of FIG. 4B, the hole of the first injection unit 201 is not shown hidden by the second injection unit 202.

4C is a bottom view of a reaction module of a vapor deposition reactor according to another embodiment. As shown, the second injection portion 202 is located within the first injection portion 201 and may be in contact with one or more of the inner walls of the first injection portion 201. However, since the first material may be injected into the substrate by the first injection part 201, the second injection part 202 may be spaced apart from at least one of the inner walls of the first injection part 201 even in this case. Should be.

4D is a bottom view of a reaction module of a vapor deposition reactor according to another embodiment. As shown, the first injection unit 201 and the second injection unit 202 may have a circular cross section, for example, may be in the form of a circular cylinder. The second injection unit 202 may be located in the first injection unit 201 to be spaced apart from the first injection unit 9201. The second material may be injected through one or more holes 3 of the second injection portion 202. In the bottom view of FIG. 4D, the hole of the first injection unit 201 is not shown hidden by the second injection unit 202.

4E and 4F are bottom views of a reaction module of a vapor deposition reactor according to still other embodiments. Referring to FIG. 4E, the second injection unit 202 may be located in the first injection unit 201 and may contact the inner wall of the first injection unit 201. Meanwhile, referring to FIG. 4F, the second injection unit 202 may be in contact with the inner wall of the first injection unit 201 in a direction different from that shown in FIG. 4E.

In addition, the cross-sectional shape of the reaction module illustrated in FIGS. 4B to 4F is exemplary, and the reaction module may have a cross section of another different shape.

5A is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment. Referring to FIG. 5A, the reaction module includes a first injector 201 and a second injector 202, wherein the first injector 201 includes a plurality of channels 2 and respective channels 2. It may be provided with a connected hole (3). By constructing a plurality of channels 2 through which the first substance is carried, it is possible to spray the first substance uniformly over a large area on the substrate 1.

FIG. 5B is a bottom view of the reaction module shown in FIG. 5A. As shown, a plurality of holes 3 are arranged at regular intervals on the bottom of the first injection unit 201 to uniformly spray the first material on the substrate. Meanwhile, in FIG. 5B, the hole 4 is a portion for the second injection portion 202 to spray the second material.

6A is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment. Referring to FIG. 6A, the reaction module includes a first injection unit 201 and a second injection unit 202, wherein the first injection unit 201 includes one or more first channels 5 and one or more second channels. (6) can be provided. Different first materials may be injected into the first channel 5 and the second channel 6. In addition, a first hole 7 and a second hole 8 may be formed in the first channel 5 and the second channel 6, respectively.

FIG. 6B is a bottom view of the reaction module shown in FIG. 6A. As shown, the first hole 7 and the second hole 8 may be alternately arranged on the bottom of the first injection unit 201. With the above configuration, it is possible to uniformly spray two different kinds of first substances on the substrate. 6A and 6B illustrate an example in which two kinds of channels 5 and 6 and two kinds of holes 7 and 8 are included for injecting two kinds of first substances, but according to the kinds of substances to be injected. And there may be more kinds of holes.

7A is a bottom view of a reaction module of a vapor deposition reactor according to another embodiment. Referring to FIG. 7A, the reaction module includes a first injector 201 and a second injector 202, wherein the second injector 202 is a first hole 4 into which different second materials are injected. And a second hole 9. The first and second holes 4, 9 can be connected to different channels from each other, which will be readily understood by those skilled in the art from the embodiment described above with reference to FIG. 6A.

7B is a bottom view of a reaction module of a vapor deposition reactor according to another embodiment. Referring to FIG. 7B, the second injection unit 202 may include a first hole 4 and a second hole 9 into which second materials different from each other are injected. In FIG. 7A, the first and second holes 4 and 9 are alternately arranged in one row, while in FIG. 7B, the first and second holes 4 and 9 may be arranged in two rows parallel to each other. have.

By configuring as in the embodiment shown in Fig. 7A or 7B, a plurality of second materials different from each other can be injected onto the substrate. For example, the raw material precursor may be injected onto the substrate through the first hole 4, and the reaction precursor may be injected onto the substrate through the second hole 9. In this case, since both the raw material precursor and the reaction precursor are injected onto the substrate passing through one reaction module, an atomic layer thin film may be formed on the substrate using one reaction module.

The arrangement of the first holes 4 and the second holes 9 shown in FIGS. 7A and 7B is exemplary, and the arrangement of the first holes 4 and the second holes 9 differs depending on the embodiment. can do. 7A and 7B illustrate an example in which two kinds of holes 4 and 9 are included to inject two kinds of second materials, but there may be more kinds of holes depending on the kinds of materials to be injected.

8 is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment.

Referring to FIG. 8, the reaction module may include a first injection unit 201, a second injection unit 202, and an exhaust unit 203. In this case, the first injection unit 201 may include the plasma generator 30 for the radical-assisted ALD, and apply the first material to the substrate 1 in the form of a plasma. The plasma generator 30 may be a variety of known types of devices and may be configured, for example, to form a plasma of the reactant gas therebetween by applying power between concentric shaped electrodes that face each other.

The first injection unit 201 of this type may be used for forming an atomic layer thin film after exciting (or decomposing) an inorganic raw material precursor, which is not easily formed by atomic layer deposition, by plasma. That is, the primary reaction (or decomposition) of the raw material precursor is induced by plasma energy and finally reacted with the reaction precursor.

For example, TiCl ₄ , which is an inorganic metal raw material, as a raw material precursor in the first injection unit 201. Alternatively, when SiH ₄ is injected and NH ₃ is injected as the reaction precursor in the second injection unit 202, a TiN or SiN thin film may be generated on the substrate 1. However, the thin film thus obtained contains not only residual Cl and residual H, but also NH ₄ Cl by the reaction of NH ₃ and Cl.

However, when TiCl ₄ is injected in the form of plasma using the first injection unit 201 as described above, since Ti atoms and Cl atoms are decomposed, Ti atoms can be adsorbed at low temperatures, thereby depositing TiN thin films. can do. In addition, when the raw material precursor mixed with TiCl ₄ and H ₂ is injected in the first injection unit 201, the incubation phenomenon or the like may be obtained because the Ti atom layer or a similar adsorption layer thereof may be obtained by plasma energy. Less adsorption reduces the deposition rate. In this case, when a forming gas of N ₂ + H ₂ is used as the reaction precursor in the second injection unit 202, a Ti thin film may be obtained on the substrate 1, and a Si thin film may be obtained in the same manner. have.

In the above embodiment, the first injection unit 201 includes the plasma generator 30, but in another embodiment, a similar effect may be obtained by providing an ultraviolet or ultra-high frequency generator in addition to the plasma.

9A is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment using plasma. Referring to FIG. 9A, the reaction module includes a first injection unit 201 and a second injection unit 202, and is located between the first injection unit 201 and the second injection unit 202 and generates plasma. The first electrode 41 and the second electrode 42 may be further included.

The first electrode 41 may be in contact with the inner wall of the first injection unit 201, and the second electrode 42 may be in contact with the inner wall of the second injection unit 202. The first and second electrodes 41 and 42 may be spaced apart from each other by a predetermined interval. When the first electrode 41 is positioned adjacent to the channel of the first injection unit 201, the first electrode 41 may include a hole for injecting the first material. The first injection unit 201 may be configured to inject a reaction gas for plasma generation together with the first material.

AC power or pulsed power may be applied between the first and second electrodes 41 and 42 by the power supply 40. The plasma is generated from the reaction gas by the power applied between the first and second electrodes 41 and 42, and radicals activated by the plasma may be applied to the substrate 1 together with the first material. Since the effect of using radicals by the plasma has been described above with reference to the embodiment shown in FIG. 8, a detailed description thereof will be omitted.

9B is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment. Referring to FIG. 9B, the first and second electrodes 41 and 42 may be positioned to apply an electric field in a direction parallel to the moving direction of the substrate 1. The first and second electrodes 41 and 42 may be provided in plural pairs. In this case, power may be applied by the power supply 40 between each of the pair of first and second electrodes 41 and 42.

According to the reaction module configured as described above, since plasma is generated directly on the substrate 1, radicals having a very short lifetime such as hydrogen radicals or nitrogen radicals can be applied to the substrate 1. In addition, since plasma is generated in a direction parallel to the surface of the substrate 1, damage to the substrate 1 by the plasma can be minimized.

In the case of using raw material precursors (eg, TiCl ₄ , SiH _4, etc.) that do not self-limiting, that is, they do not saturate during chemisorption, the number of cycles is increased in conventional reactors. There was only one way to form an atomic layer. However, using the vapor deposition reactor according to the embodiments, the surface activation by the plasma induces the adsorption of sufficient precursor precursors, so that no nucleation step is required, and the atomic layer thin film does not have an incubation phenomenon. Can be obtained.

10 is a cross-sectional view of a vapor deposition reactor according to another embodiment. Referring to FIG. 10, the reaction module 20 of the vapor deposition reactor includes a plurality of first injection units 201 and 211 and a plurality of second injection units 202 located in each of the first injection units 201 and 211. , 212). The plurality of first injection units 201 and 211 and the second injection units 202 and 212 may be located in one exhaust unit 203.

An example of a thin film formation process using the vapor deposition reactor configured as described above will be described. When the substrate 1 moved from the left side flows into the lower portion of the reaction module 20, impurities or adsorbates on the substrate 1 may be removed by the exhaust part 203. When the substrate 1 moves further to the right and positioned below the first injection unit 201, the first material may be injected onto the substrate 1 by the first injection unit 201. In this case, the first material may be a purge gas.

When the substrate 1 moves further to the right and positioned below the second injection portion 202, the second material may be injected onto the substrate 1 by the second injection portion 202. For example, the second injection unit 202 may inject the reaction precursor onto the substrate 1. The substrate 1 passing through the second injection unit 202 may sequentially pass through the first injection unit 201 and another first injection unit 211. In this process, the substrate 1 may be formed on the substrate 1 again. 1 substance may be injected.

When the substrate moves further to the right and positioned below the second injection portion 212, a second material may be injected onto the substrate 1 by the second injection portion 212. For example, the second injection unit 212 may inject the raw material precursor onto the substrate 1. In this case, the chemical adsorption layer of the reaction precursor injected by the second injection unit 202 and the raw material precursor injected by the second injection unit 212 are replaced and / or reacted to form a thin film on the substrate 1. Can be. When the substrate 1 moves further to the right, the substrate 1 may completely pass through the reaction module 20 through the first injection part 211 and the exhaust part 203.

That is, while passing through the reaction module 20, the substrate 1 is injected with the first material-> injection of the second material (reactive precursor)-> injection of the first material-> second material (raw precursor)-> first material Five steps of implantation are performed, and as a result, a thin film may be formed on the substrate 1. In addition, a pumping step by the exhaust unit 203 may be added before or after the above five steps.

The first injection parts 201 and 211 and the second injection parts 211 and 212 illustrated in FIG. 10 may be configured according to any of the above-described embodiments with reference to FIGS. 2 to 9. That is, one or more of the first injection units 201 and 211 may include a plasma generator, and one for generating plasma between each of the first injection unit-second injection unit pairs 201-211 and 202-212. The above electrode may be included. In addition, one or more of the first injection parts 201 and 211 and the second injection parts 211 and 212 may include a plurality of channels and holes. The configuration of one first injection unit 201 and the other first injection unit 211 may be different from each other, and similarly, the configuration of one second injection unit 211 and another second injection unit 212 may be different from each other. It may be different.

Since the vapor deposition reactor according to the embodiments described above is configured such that at least one second injection unit is positioned in the first injection unit of the reaction module, a plurality of materials different from each other by the first injection unit and the second injection unit may be formed. Can be injected into. Accordingly, a thin film may be formed by injecting a raw material precursor or a reaction precursor into the substrate without exposing the substrate to an atmosphere in the chamber. The vapor deposition reactor may be used for ALD.

Although the present invention described above has been described with reference to the embodiments illustrated in the drawings, this is merely exemplary, and it will be understood by those skilled in the art that various modifications and variations may be made therefrom. However, such modifications should be considered to be within the technical protection scope of the present invention. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

1 is a flowchart illustrating an atomic layer deposition method according to the prior art.

2 is a schematic perspective view of a vapor deposition reactor according to one embodiment.

3A is a cross-sectional view of a vapor deposition reactor according to one embodiment.

FIG. 3B is a partially enlarged view of the vapor deposition reactor shown in FIG. 3A.

3C and 3D are cross-sectional views of a reaction module of a vapor deposition reactor according to other embodiments.

3E is a cross-sectional view of a vapor deposition reactor according to another embodiment.

4A is a side cross-sectional view of a first reaction module of a vapor deposition reactor according to one embodiment.

4B-4F are bottom views of a reaction module of a vapor deposition reactor according to embodiments.

5A is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment.

FIG. 5B is a bottom view of the reaction module shown in FIG. 5A.

6A is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment.

FIG. 6B is a bottom view of the reaction module shown in FIG. 6A.

7A and 7B are bottom views of a reaction module of a vapor deposition reactor according to still other embodiments.

8 is a cross-sectional view of a reaction module of a vapor deposition reactor according to another embodiment.

9A and 9B are cross-sectional views of a reaction module of a vapor deposition reactor according to still other embodiments.

10 is a cross-sectional view of a vapor deposition reactor according to another embodiment.

Claims (18)

An exhaust unit for discharging the substance to the outside; A first injection part positioned in the exhaust part and injecting a first material including a purge gas into the substrate; And A reaction module positioned in the first injection portion and including at least one second injection portion for injecting a second material including a reaction precursor or a raw material precursor into a substrate; The reaction module has a structure in which the substrate passes through the reaction module due to relative movement with the substrate, The vapor deposition reactor, characterized in that the distance between the first injection portion and the second injection portion along the moving direction of the substrate is adjustable. delete The method of claim 1, And a chamber in which one or more said reaction modules are located. delete The method of claim 1, Wherein said purge gas comprises any one selected from the group consisting of N ₂ , Ar and He, or a combination of two or more thereof. The method of claim 1, The reaction module includes a plurality of reaction modules, And the second injector of the plurality of reaction modules inject a plurality of second materials different from each other into a substrate. The method of claim 6, And the plurality of second materials react or substitute with each other to form a thin film on the substrate. The method of claim 1, The one or more second injection portions include a plurality of second injection portions, And the plurality of second injectors respectively inject a plurality of second materials different from each other into a substrate. The method of claim 8, And the plurality of second materials react or substitute with each other to form a thin film on a substrate. The method of claim 1, And a gap between the first injection portion and the one or more second injection portions is determined based on deposition characteristics of the thin film formed by the vapor deposition reactor. delete The method of claim 1, The reaction precursor is H ₂ O, H ₂ O ₂ , O ₂ , N ₂ O, O ₃ , O * radicals, NH ₃ , NH ₂ -NH ₂ , N ₂ , N * radicals, CH ₄ , C ₂ H Vapor deposition reactor comprising at least one selected from the group consisting of ₆ , H ₂ and H * radicals or a combination of two or more thereof. The method of claim 1, The raw material precursor is a group IV compound, III-V compound, II-VI compound, Ni compound, Co compound, Cu compound, Al compound, Ti compound, Hf compound, Zr compound, Ta A vapor deposition reactor comprising any one selected from the group consisting of a compound, an Mo compound, a W compound, a Si compound, and a Zn compound, or a combination of two or more thereof. The method of claim 1, The first injection unit vapor deposition reactor characterized in that it comprises a plasma generator, ultra-high frequency generator or ultraviolet generator. The method of claim 1, The reaction module, And one or more electrodes positioned between the first injection portion and the second injection portion for generating a plasma. The method of claim 15, Wherein said at least one electrode is positioned to apply an electric field in a direction parallel to the direction of movement of the substrate. The method of claim 1, The first injection portion and the second injection portion, One or more channels in the shape of a straight pipe; And And one or more holes formed in each of the one or more channels. The method of claim 17, And said at least one channel comprises a first channel and a second channel into which different materials are injected.

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