KR102165482B1 - plasma chemical vapor deposition apparatus using laser and the method thereof - Google Patents

Abstract

The present invention relates to a plasma chemical vapor deposition apparatus, and more particularly, to a laser plasma chemical vapor deposition apparatus capable of forming a high-quality deposition layer even at a low temperature during chemical vapor deposition.
An embodiment of the present invention, a laser generator; An optical system unit for adjusting the focus and path of the laser generated by the laser generating unit; And a chamber unit for performing plasma chemical vapor deposition on a substrate to be deposited with a reactive material by spraying a reactive material on a path of the laser output from the optical system unit, wherein the laser is in a horizontal direction with the substrate in the chamber unit It provides a laser plasma chemical vapor deposition apparatus, characterized in that configured to be irradiated.

Description

TECHNICAL FIELD [0001] Plasma chemical vapor deposition apparatus using laser and the method thereof

The present invention relates to a plasma chemical vapor deposition apparatus, and more particularly, to a laser plasma chemical vapor deposition apparatus and method capable of forming a high-quality deposition layer even at a low temperature during chemical vapor deposition.

The CVD (chemical vapor deposition) method refers to a chemical vapor deposition method and uses the principle of depositing a thin film on a substrate in a chamber through high-temperature decomposition or high-temperature chemical reaction by spraying a gas or liquid of a material to be deposited on a substrate. This method has excellent adhesion between the substrate and the deposited thin film, can produce a uniform thin film regardless of the shape of the substrate, and is an easy method for depositing a high-purity material.

For this reason, it is also the most widely used method in the current semiconductor manufacturing process and OLED display manufacturing.

Among the CVD methods, the laser chemical vapor deposition method (LACVD) among the CVD methods forms a thin film by injecting a reactant into the chamber where the substrate is located and then irradiating a laser to cause the reactant to undergo a chemical reaction with the substrate to be deposited on the substrate. That's how to do it.

In addition, in the plasma chemical vapor deposition (PECVD), a reaction material such as a reaction gas required for deposition or a liquid containing a reactant is injected into a chamber that forms a vacuum, and when the desired pressure and substrate temperature are set, the electrode is at an ultra-high frequency. This is a method of forming a thin film by applying a reaction material to a plasma state by applying a reaction material or a precursor to ionize the ionized precursor and a part of the plasma state reaction material to be deposited on the substrate through a physical or chemical reaction.

In order to increase the efficiency of the plasma chemical vapor deposition method, a number of studies have been conducted on a method of performing deposition by using a laser in parallel. As a result of these studies, Korean Patent Laid-Open No. 2018-0068637 and Korean Patent No. 1243782 disclose a chemical vapor deposition apparatus using a laser that forms a thin film on a substrate by irradiating a laser and forming a plasma after supplying a reactant. Are doing.

However, the above-described plasma chemical vapor deposition method using a laser has a problem in that when the deposition temperature of the substrate is lowered, the reactant is not sufficiently decomposed, so that the quality of the deposited thin film is degraded, so that the deposition temperature is lowered.

In addition, in the case of the above-described laser chemical vapor deposition method, the deposition temperature can be lowered, but the deposition rate is slow and it is difficult to uniformly irradiate the laser. On the contrary, when the laser power is increased to increase the deposition rate , Since the laser is irradiated toward the substrate, there is a problem that the substrate may be damaged by the laser.

Republic of Korea Patent Publication No. 2018-0068637 Korean Registered Patent No. 12443782

Accordingly, an embodiment of the present invention for solving the problems of the prior art described above is, in performing plasma chemical vapor deposition, by irradiating a laser so that energy is uniformly dispersed throughout the reactant to improve the reactivity of the reactant. A laser plasma chemical vapor deposition device suitable for thin film deposition of various materials including organic materials, which improves the deposition rate on the substrate while lowering the deposition temperature for vapor deposition and significantly improves the quality of the deposited thin film. And to provide a method thereof.

An embodiment of the present invention for achieving the above object, a laser generator; An optical system unit for adjusting the focus and path of the laser generated by the laser generating unit; And a chamber unit for performing plasma chemical vapor deposition on a substrate to be deposited with a reactive material by spraying a reactive material onto the path of the laser output from the optical system unit, wherein the laser whose focus and path are adjusted in the optical system unit is the It provides a laser plasma chemical vapor deposition apparatus, characterized in that irradiated into the interior of the chamber.

The laser according to an embodiment of the present invention may be configured to be irradiated into the chamber from both sides of the chamber.

The laser output from the laser generator according to an embodiment of the present invention may have a wavelength in the range of 150 to 20,000 nm.

The laser output from the laser generator according to the embodiment of the present invention may have a power density in the range of 0.001 to 100 W/mm ² on the substrate in the deposition chamber.

The optical system unit according to an embodiment of the present invention includes a multifocal optical system having a multi-segment lens for converting the laser into a multi-line laser by dividing the laser into a plurality of lines at predetermined intervals in a lateral direction of the laser irradiation direction. It can be configured.

The optical system unit according to an embodiment of the present invention selectively moves the laser to a z-axis perpendicular to the laser irradiation direction, a y-axis that is the laser irradiation direction, and an x-axis horizontal to the laser irradiation direction, It may be configured to include a laser irradiation driving unit for irradiating a scan or vibration into the interior of the chamber unit.

The laser irradiation driving unit according to an embodiment of the present invention may be configured to vibrate the laser in the x-axis direction during scan irradiation of the laser.

The laser irradiation driving unit according to an embodiment of the present invention may be configured to vibrate the laser in the z-axis direction during scan irradiation of the laser.

The optical system unit according to an embodiment of the present invention may be configured to have an irradiation area corresponding to an area obtained by dividing the length of the substrate into a predetermined interval by dividing the laser, and scan and irradiate the entire length of the substrate for each irradiation area. I can.

The chamber unit according to an embodiment of the present invention includes: a chamber; A reaction material supply unit formed above the chamber to supply a reactant material into the chamber; A showerhead installed under the reactant supply unit, having a cathode, and spraying the reactant material evenly to the substrate side; A plasma energy generator for supplying plasma energy to the interior of the chamber to convert the reaction material injected into the chamber into plasma; And a susceptor disposed under the Shawe head to support the substrate and acting as an anode.

The plasma energy generator according to an embodiment of the present invention may be configured to irradiate the reaction material with a plasma energy density in the range of 0.01 W/cm ² to 10 W/cm ² .

Another embodiment of the present invention for achieving the above object is a chamber unit, a reactant supply unit, a shower head, a plasma energy generation unit, and a susceptor that is disposed to support the substrate under the Shawe head and acts as an anode. A chemical vapor deposition method using a laser plasma chemical vapor deposition apparatus comprising: a reactant spraying step of injecting a reactant into a chamber through the reactant supply unit; Plasmaizing the reactant material into plasma by supplying plasma energy into the chamber through the plasma energy generator; And a laser irradiation step of irradiating a laser output from the laser generating unit into the interior of the chamber unit at the same time as the plasma forming step to promote a plasma reaction of the reactants supplied to the interior of the chamber unit. It provides a laser plasma chemical vapor deposition method.

The laser irradiation step according to another embodiment of the present invention may be a step of irradiating the laser into the chamber from both sides of the chamber.

In the laser irradiation step according to another embodiment of the present invention, the laser is divided into a plurality of lines at predetermined intervals in a lateral direction of the laser irradiation direction by a multi-segment lens provided in the optical system unit to form a multi-line laser. It may be a step of converting and investigating.

The laser irradiated in the laser irradiation step according to another embodiment of the present invention may have a wavelength in the range of 150 to 20,000 nm.

The laser irradiated in the laser irradiation step according to another embodiment of the present invention may have a power within a range of 0.001 W/cm ² to 100 W/mm ² on the substrate in the chamber.

The plasmaizing step according to another embodiment of the present invention may be to supply plasma energy having a plasma energy density of 0.01 W/cm ² to 100 W/cm ² in order to plasmaize the reactant.

The laser plasma chemical vapor deposition apparatus according to the above-described embodiment of the present invention accelerates plasma conversion of the reactant by irradiating a laser from the side direction of the reactant during plasma chemical vapor deposition to reduce unreacted gas. It provides the effect of allowing high-quality thin films to be deposited on a substrate while lowering the chemical vapor deposition temperature.

The laser plasma chemical vapor deposition apparatus according to an embodiment of the present invention described above further accelerates the plasma conversion of the reactant by irradiating a laser from both directions of the reactant during the plasma chemical vapor deposition to further reduce unreacted gas. Accordingly, while lowering the plasma chemical vapor deposition temperature, the substrate deposition rate of the reactant material is increased, and a more uniform high-quality thin film can be deposited.

The laser plasma chemical vapor deposition apparatus according to an embodiment of the present invention described above provides high efficiency and high quality thin film deposition of various materials including organic materials by increasing the substrate deposition rate of reactants while lowering the plasma chemical vapor deposition temperature. It provides an effect that allows it to be performed with.

1 is a partial plan sectional view of a LAPECVD: Laser Assisted Plasma Enhanced Chemical Vapor Deposition (LAPECVD) 1 according to an embodiment of the present invention.
2 is a laser plasma chemical vapor phase showing a connection configuration between the laser generator 100, the optical system 200, and the chamber 300 for irradiating the laser of the laser generator 100 into the chamber 300 Partial perspective view of the deposition apparatus.
3 is a diagram showing the configuration of a multifocal optical system 220 according to an embodiment of the present invention.
4 is a partial cross-sectional view of an optical device unit 200 for showing the laser irradiation driving unit 210 according to an embodiment of the present invention.
5 is a photograph showing an actual implementation example of the laser irradiation driving unit 210 of FIG. 4.
6 is a plan partial cross-sectional view of the chamber unit 300 of FIG. 1 showing bidirectional irradiation of a multi-laser.
7 is a side cross-sectional view cut in a direction crossing the laser ports 350 on both sides of the chamber unit 300 of FIG. 1.
8 is a graph comparing water vapor transmission rate (WVTR) characteristics of a thin film formed by laser plasma chemical vapor deposition (LAPECVD) and plasma chemical vapor deposition (PECVD) according to an embodiment of the present invention.
9 is a thin film formed by irradiating from one side of the chamber 300 while scanning a laser beam from side to side during laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention and plasma chemical vapor deposition (PECVD) of the prior art. A graph showing the uniformity of the thin film formed by
10 is a photograph of a thin film TF formed by irradiating from one side of the chamber 300 while scanning a laser beam from side to side during laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention.
11 formed by a thin film (TF) formed by irradiating both sides of a laser plasma chemical vapor deposition (LAPECVD) chamber 300 simultaneously in both directions according to an embodiment of the present invention and a plasma chemical vapor deposition (PECVD) of the prior art A graph measuring the thickness change by location of the thin film (TF).
12 is a photograph of a thin film TF formed by simultaneously irradiating both sides of a laser plasma chemical vapor deposition (LAPECVD) chamber 300 according to an embodiment of the present invention in both directions.
13 is a flow chart showing a processing process of a laser plasma chemical vapor deposition method according to another embodiment of the present invention.

In the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

Since the embodiments according to the concept of the present invention can apply various changes and have various forms, specific embodiments will be illustrated in the drawings and described in detail in the present specification or application. However, this is not intended to limit the embodiments according to the concept of the present invention to a specific form of disclosure, and the present invention should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

When a component is referred to as being "connected" or "connected" to another component, it is understood that it may be directly connected or connected to the other component, but other components may exist in the middle. Should be. On the other hand, when a component is referred to as being "directly connected" or "directly connected" to another component, it should be understood that there is no other component in the middle. Other expressions describing the relationship between components, such as "between" and "just between" or "adjacent to" and "directly adjacent to" should be interpreted as well.

The terms used in this specification are used only to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of a set feature, number, step, action, component, part, or combination thereof, but one or more other features or numbers It is to be understood that the possibility of addition or presence of, steps, actions, components, parts, or combinations thereof is not preliminarily excluded.

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

1 is a partial plan view of a laser plasma chemical vapor deposition apparatus 1 according to an embodiment of the present invention, and FIG. 2 is a laser for irradiating the laser of the laser generating unit 100 into the interior of the chamber unit 300 It is a partial perspective view of a laser plasma chemical vapor deposition apparatus showing a connection configuration between the generation unit 100 and the optical system unit 200 and the chamber unit 300.

As shown in FIG. 1, the laser plasma chemical vapor deposition apparatus 1 according to an embodiment of the present invention receives the output laser L of the laser generating unit 100 and the laser generating unit 100, and then adjusting the focus. And a plasma chemical vapor phase on the substrate by spraying a reactive material on the path of the optical system unit 200 that irradiates the interior of the chamber unit 300 by adjusting the optical path and the laser L output from the optical system unit 200. Consisting of a chamber unit 300 for performing deposition, the laser is irradiated in the lateral direction of the plasmad reaction gas inside the chamber unit 300 to convert the unreacted reaction material into plasma to form a laser plasma chemical vapor phase. A thin film is laminated on the substrate charged in the chamber unit 300 by performing laser assisted plasma enhanced chemical vapor deposition (LAPECVD).

The laser generator 100 is ArF (193 nm) A laser can be provided. In addition, the wavelength of the laser L generated by the laser generating unit 10 may have a range of 150 to 20,000 nm. This has a disadvantage in that when the wavelength of the laser L is less than 150 nm, the cost of the laser L itself increases too much, so that the production cost increases and it is difficult to form high power. In addition, when the irradiation wavelength of the laser unit 10 is more than 20,000 nm, energy of the laser irradiated to form the dense thin film 71 may be insufficient due to a long wavelength laser having low energy.

In addition, the laser L generated by the laser generator 100 may be irradiated by adjusting the power density on the substrate inside the chamber to have a range of 0.001 W/cm ² to 100 W/mm ² . When the power of the laser L is less than 0.001 W/mm ² , the power of the laser energy is too low, and gas decomposition may not occur effectively. In addition, when the power of the laser L output from the laser unit 10 exceeds 100 W/mm ² , the production cost may increase due to an increase in laser cost.

The optical system unit 200 is configured to include a plurality of convex, concave, or fly lenses and reflectors for adjusting the path and focus of the laser L, and output from the laser generating unit 100 It may be configured to irradiate the resulting laser (L) into the interior of the chamber 300 from the side direction of the chamber 300. In this case, the optical system unit 200 may be configured to have a double laser path so that the laser L is simultaneously irradiated into the chamber unit 300 from both sides of the chamber unit 300.

The optical system unit 200 is configured to convert the laser into a multi-line laser (ML) having a plurality of laser lines and irradiate it, and to change the irradiation direction in the vertical, horizontal and traveling direction of the multi-line laser (ML). May be.

3 is a diagram showing the configuration of a multifocal optical system 220 according to an embodiment of the present invention, and FIG. 4 is an optical device unit 200 for showing the laser irradiation driving unit 210 according to an embodiment of the present invention. ) Is a partial cross-sectional view, and FIG. 5 is a photograph showing an actual implementation example of the laser irradiation driving unit 210 of FIG. 4.

In FIG. 3, (a) is a diagram showing a multi-laser irradiation driving state, (b) is a photograph of an actual implementation example of the multifocal optical system 220, and (c) is a multi-segmented multifocal optical system 220 The focus (LP) picture of the laser (ML) is shown.

As shown in (b) of FIG. 3, the multifocal optical system 220 includes a multi-split lens 230 for forming the laser L into a multi-line laser ML having a plurality of focuses, and a multi-split lens It is configured to include a lens holder 231 for fixing the 230. In this case, the multi-split lens 230 may be a fly lens or the like in which lenses having a plurality of focal points are arranged.

The multifocal optical system 220 having the above-described configuration receives the laser L output from the laser generating unit 100 through the reflective mirror 201, as shown in FIG. It is converted into a multi-line laser (ML) having a plurality of laser lines going to and outputted. The multi-line laser (ML) converted in this way is divided at predetermined intervals along the x-axis direction, which is the horizontal direction of the laser irradiation direction, on a surface parallel to the substrate surface on which laser plasma chemical vapor deposition is to be performed, as shown in Fig. 3(c). It has a number of focal points (LP). Accordingly, the area of laser irradiation to the reactant material in the x-axis direction inside the chamber unit 300 is increased, and a multi-line laser in the divided width area by scanning and irradiating a multi-line laser (ML) in the x-axis direction (ML) is superimposed irradiation to improve the plasma conversion efficiency of the reactant.

As shown in Figure 4, the laser irradiation driver 210 is equipped with a single focus optical system (not shown) or the multifocal optical system 220, and is configured to move the single focus optical system or the multifocal optical system along the y-axis direction. The y-axis driving unit (ym) and the y-axis driving unit (y) installed under the y-axis driving unit (y) to move the y-axis driving unit (ym) in the x-axis direction (xm) and the y-axis driving unit (yn) It is configured to include a z-axis driving unit (zm) installed below the x-axis driving unit (xm) so as to simultaneously elevate the x-axis driving unit (xm) in the vertical direction. At this time, the x-axis is a horizontal direction with respect to the irradiation direction of the laser (L) or multi-line laser (ML), the y-axis is the irradiation direction of the laser (L) or the multi-line laser (ML), and the z-axis is the laser (L) or the It is set in the vertical direction of the multi-line laser (ML) irradiation direction.

The laser irradiation driving unit 210 having the configuration of FIG. 4 described above is the single focus optical system or the single focus optical system by selectively moving in the three-axis directions of the x, y, and z axes of the single focus optical system or the multifocal optical system 220 The irradiation direction, scan direction, or horizontal-vertical vibration of the single-focus laser irradiated through the multifocal optical system 220 or the multi-line laser (ML) divided into a plurality of lines and irradiated is adjusted.

The laser generating unit 100 and the optical system unit 200 having the above-described configuration, in order to further improve the plasma efficiency of the reaction material injected from the inside of the chamber unit 300, as shown in FIG. 6 to be described below. To be able to simultaneously irradiate the laser (L) or multi-line laser (ML) having a single focus from both sides of the reaction material inside the chamber unit 300, as shown in Figure 1, it will be configured double on both sides of the chamber unit 300 May be. At this time, the laser irradiated from both sides has the same energy and is irradiated from both sides, so that even if it is absorbed inside the chamber unit 300, the entire reactant is irradiated with as uniform energy as possible, so that plasma of the reactants is uniformly achieved. have.

And the laser irradiated from both sides of the chamber unit 300 is generated in one laser generating unit 200 through one laser generating unit 100 and two optical system units 20, unlike the configuration of FIG. The resulting laser may be divided into two paths by the two optical system units 200 to be irradiated. In this case, the laser irradiated from both sides of the chamber unit 300 in consideration of loss of laser energy due to air in the optical path through which the laser passes by dividing and irradiating the laser energy with the larger optical path Can be configured to be irradiated in both directions so that they overlap each other with the same or similar intensity.

As described above, when a laser (L) or a multi-line laser (ML) is irradiated into the interior of the chamber part 300 from both sides of the chamber part 300, the laser (L) or the multi-line laser (ML) is It can be configured to prevent excessive laser energy from being supplied to the reactant by being divided to have a size in the range of 0.4 to 0.6 of the laser power required for plasmaization.

Next, the configuration of the chamber unit 300 of FIG. 1 will be described.

6 is a plan partial cross-sectional view of the chamber unit 300 of FIG. 1 showing bidirectional irradiation of a multi-laser, and FIG. 7 is cut in a direction crossing the laser ports 350 on both sides of the chamber unit 300 of FIG. 1 It is a side cross-sectional view.

As shown in FIGS. 6 and 7, the chamber unit 300 is installed under the reaction material supply unit 320 at the upper portion and the reaction material supply unit 320 constituting the chamber 310, and has a cathode and has a reaction material. A plasma energy generator that supplies high frequency, which is plasma energy, to a showerhead 330 that evenly distributes and sprays the plasma, and a coil configured inside the chamber 310 to convert the reactant material injected into the chamber 310 into plasma. 340, the susceptor 350, which is disposed to support the substrate S under the Shawe head 330 and acts as an anode, and a laser L or a multi-line laser ML of the chamber 310 are irradiated. It is configured to include one or a pair of laser ports 360 installed on one or both sides.

The reactant supply unit 320 is configured to supply the reactant material to a space in the chamber 310 to perform laser plasma chemical vapor deposition. The reactants injected into the chamber part 300 are argon (Ar), helium (He), krypton (Kr), xenon (Xe), neon (Ne), silicon hydride (SiH ₄ , Si ₂ H ₄ ) , Nitric oxide (N ₂ O), oxygen (O ₂ ), nitrogen (N ₂ ), ammonia (NH ₃ ) reaction gas, or a liquid such as Trimethylaluminum (TMA), H ₂ O.

The showerhead 330 is configured to disperse and spray the reactants so that the incoming reactants are uniformly sprayed on the upper portion of the substrate S. Then, the plasma-generated reactant is transferred to the substrate S to form a thin film.

The plasma energy generation unit 340 is configured to supply plasma energy into the chamber 310 by applying a high frequency to a coil or the like configured in the chamber 310.

The plasma energy supply unit 340 is an RF unit, a match, and a chamber 310 for forming a high frequency or electric field in the inner space of the chamber 310 for plasmaizing the reactants injected into the chamber 310. ) It may be configured to include an antenna or electrode rod formed inside. In this case, the plasma energy density supplied from the plasma energy supply unit 340 may have a range of 0.01 W/cm ² to 10 W/cm ² . This is because when the plasma energy density is 0.01 W/cm ² or less, sufficient plasma may not be formed, and when the plasma energy density is 10 W/cm ² or more, the uniformity of the thin film may be reduced due to excessive plasma formation.

The susceptor 350 is disposed to face the shower head 330 at the bottom of the shower head 330 and supports the substrate S, and a positive potential is applied to transfer negative ions in the plasma to the substrate S. It is configured to deposit on the surface.

The laser port 360 functions as a window for receiving the laser L or the multi-line laser ML irradiated from the optical system unit 200 into the interior of the chamber unit 300. To this end, the laser port 350 is provided with one or more air curtain tubes on the upper side of the interior, so that the optical system unit 200 from the side where the laser (L) or multi-line laser (ML) of the chamber unit 300 is incident. It may be configured to include a tubular laser port case mounted to protrude into and a laser irradiation window installed at an end opening of the laser port case. In this case, the laser irradiation window may be formed to have a width greater than the width of the target substrate for thin film formation so that the laser (L) or the multi-line laser (ML) scan irradiation can be performed on the entire upper area of the substrate. have.

The air curtain tube prevents plasmaized reactants from depositing on the irradiation window. By spraying non-reactive gases such as nitrogen or argon gas into the irradiation window in a downward-facing diagonal direction, the plasmaized reactant material is transferred to the irradiation window. It may be configured to form an air curtain that prevents movement.

In the laser plasma chemical vapor deposition apparatus 1 according to an embodiment of the present invention having the above-described configuration, after mounting the substrate S inside the chamber unit 300, after spraying a reactant, plasma energy is supplied to the plasma. In the process of performing chemical vapor deposition, the laser output from the laser generating unit 100 is converted to a laser (L) or a multi-line laser (ML) whose focus and path are adjusted through the optical system unit 200 to convert the chamber unit ( By irradiating the reactants inside the chamber 310 from the side direction of 300), unplasmaized reactants are converted into plasma to improve the plasma efficiency of the reactants, thereby increasing the efficiency of plasma chemical vapor deposition. Provides an enhancing effect.

At this time, in order to improve the efficiency of plasma chemical vapor deposition, the laser (L) or the multi-line laser (ML) is scanned in the horizontal direction (x-axis) of the irradiation direction by the laser irradiation driver 210 of the optical system unit 200. Irradiation, vibration in the vertical direction (z-axis) direction, scan irradiation in the horizontal direction (x-axis), scan irradiation in the horizontal direction (x-axis), and vibration irradiation in the horizontal direction (x-axis) simultaneously By performing the vibrating scan irradiation, it is possible to further significantly improve the plasma conversion efficiency of the reactant material while lowering the plasma conversion temperature, thereby providing an effect of further remarkably improving the efficiency of plasma chemical vapor deposition.

In addition to this, as shown in FIGS. 1 and 6, by irradiating the focused laser (L) or multi-line laser (ML) from both sides of the chamber unit 300 while scanning left and right, a uniform laser is applied to the entire reaction material. By irradiating energy, it provides an effect of further improving the efficiency of plasmaization of the reactant and the efficiency of plasma chemical vapor deposition. In this case, when the substrate is large-area, when the laser (L) or multi-line laser (ML) is scanned left and right and irradiated in a single direction, the laser energy varies according to the distance within the chamber due to the absorption of the laser. Uniformity is lost, making it impossible to perform uniform thin film deposition. Therefore, it is preferable to irradiate the laser in both directions when depositing a thin film on a large-area substrate having a size larger than that in which the uniformity of laser energy in the large-area chamber is broken.

<Experimental Example>

8 is a graph showing a comparison graph of water vapor transmission rate (WVTR) characteristics of a thin film formed by laser plasma chemical vapor deposition (LAPECVD) and plasma chemical vapor deposition (PECVD) according to an embodiment of the present invention.

The measurement of the water vapor transmission rate (WVTR) characteristic of FIG. 8 is performed by applying an optical system that changes the beam size with a laser power of 75mW/mm ² and 80mm x 5mm using the conditions of <Table 1> below. It was carried out using substrates having a thin film formed by laser plasma chemical vapor deposition (LAPECVD) and plasma chemical vapor deposition (PECVD) of the prior art.

<Table 1>

WVTR was measured for a substrate having a thickness of 300 nm among the substrates on which the thin film was deposited under the above-described conditions. In FIG. 8, (a), (b) and (c) are in the plasma chemical vapor deposition (PECVD) of the prior art. Is a graph showing the WVTR measurement results of substrates having a thin film formed by, (d), (e) and (f) are WVTR of substrates having a thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention A graph showing the measurement result is shown.

As in the comparison of the graph of Fig. 8, when compared with (a), where the thin film was formed by PECVD of the prior art under the same conditions, about 53% or more in the case of (d) the thin film was formed by LAPECVD of the embodiment of the present invention. It showed a decrease in water permeability. In addition, when compared with (b) in which the thin film was formed by PECVD of the prior art under the same conditions, (e) in which the thin film was formed by LAPECVD of the embodiment of the present invention showed a decrease in water transmittance of about 57% or more. In addition, when compared to (c) in which the thin film was formed by PECVD of the prior art under the same conditions, in the case of (f) formed by laser plasma chemical vapor deposition (LAPECVD) of the embodiment of the present invention, about 46% or more moisture It showed a decrease in transmittance. That is, in the case of the thin films formed by laser plasma chemical vapor deposition (LAPECVD) of the embodiment of the present invention, compared to the thin films formed by plasma chemical vapor deposition (PECVD) of the prior art, the moisture transmittance is reduced by about 45% to 55%. Showed. This is a result of the supply of plasma energy and the additionally irradiated lasers incidentally decomposing the reaction gas to obtain a thin film with excellent properties.

9 and 10 show a thin film formed by irradiating from one side of the chamber 300 while scanning a laser beam from side to side during laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention under the conditions of [Table 2]. A graph showing the uniformity of a thin film formed by plasma chemical vapor deposition (PECVD) of the prior art and a photograph of a thin film formed by an embodiment of the present invention.

[Table 2]

9 and 10, a laser having a power of 2 W/mm ² , a scanning irradiation speed of 20 mm/s, and a beam size of 5 x 3 mm ² during laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention is used in the chamber. One side of 300 was irradiated in one direction to deposit a thin film, and the deposited thin film was rotated 180 degrees to deposit once more to form a thin film (TF).

As a result of measuring the thickness of each location after the thin film (TF) was deposited, the thickness of the thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention was determined by the conventional plasma chemical vapor deposition (PECVD). It was thicker than the thickness of the thin film formed by However, in the case of a thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention, it was confirmed that the thickness for each location was changed to ±5.5% as the distance from the laser port 460 increased. This is considered to be due to the fact that the laser energy is absorbed by the reactant and decreases as the distance from the laser port 460 increases.

11 and 12 are a thin film (TF) formed by irradiating both sides simultaneously from both sides of a laser plasma chemical vapor deposition (LAPECVD) chamber 300 according to an embodiment of the present invention under the conditions of [Table 2] and the prior art. This is a graph measuring the thickness change of the thin film TF formed by the plasma chemical vapor deposition (PECVD) of each location and a photograph of the thin film TF formed according to the embodiment of the present invention.

In the case of FIGS. 11 and 12, laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention controls a laser with a power of 2 W/mm ² , a scan irradiation speed of 20 mm/s, and a beam size of 5 x 3 mm ² . A thin film was deposited by irradiating simultaneously in both directions from both sides of the chamber 300 while scanning with, and the formed thin film TF was rotated 180 degrees to perform another process to deposit the thin film TF.

As a result of measuring the thickness of each location after the thin film (TF) was deposited, the thickness of the thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention was determined by the conventional plasma chemical vapor deposition (PECVD). It was thicker than the thickness of the thin film formed by In addition, in the case of a thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention, it can be confirmed that the change in thickness is uniform at ± 1.4% even when the thickness for each location is away from the laser port 460. there was. This is because the laser energy irradiated in one direction is absorbed by the reactant material and decreases as the distance from the laser port 460 increases, but the laser irradiated in the other direction supplements the reduced energy in the entire area inside the chamber 310. This is because the uniformity of laser energy is ensured.

13 is a flow chart showing a processing process of the laser plasma chemical vapor deposition method of the present invention.

As shown in FIG. 13, the above-described laser plasma chemical vapor deposition method performs a reactant spraying step (S10) of spraying a reactant into the interior of the chamber unit 300, so that the chamber portion in which the substrate to be deposited S is mounted. Inject a reactant inside.

Thereafter, plasma energy such as high frequency is supplied through the plasma energy generating unit 370 inside the chamber unit 300 to perform a plasma conversion step of converting the reaction material into plasma.

In the case of performing the plasmaization step, plasma energy such as a high frequency or electric field is supplied and at the same time, a laser output from the laser generating unit 100 is in a horizontal direction with the substrate S inside the chamber unit 300. By performing a laser irradiation step (S30) of irradiating the inside of the chamber unit 300 through the optical system unit 200 to promote the plasma reaction of the reactive material, the reactive material on the substrate S Is deposited by laser plasma chemical vapor deposition.

During the above-described processing, the laser irradiation step (S30) is performed by the multi-segment lens 230 provided in the optical system unit 200 in a lateral direction of the laser irradiation direction to a plurality of lines at predetermined intervals. It may be a step of dividing and converting it to a multi-line laser (ML) for irradiation.

In another embodiment of the present invention, the laser irradiation step (S30) includes the laser generating unit 100 and the optical system unit 200 in duplicate, so that the chamber unit 300 at both sides of the chamber unit 300 ) It may be a step of irradiating a laser inside. In this case, when the laser is irradiated from both sides of the chamber unit 300, the laser may be controlled to have a power of 1/2 of the laser when irradiating the laser from one side direction of the chamber unit 300. .

Another embodiment of the present invention for achieving the above object is characterized in that it provides a substrate on which a laser plasma chemical vapor deposition thin film is deposited by the laser plasma chemical vapor deposition method.

The substrate on which the laser plasma chemical vapor deposition thin film is deposited may have a water vapor transmission rate (WVTR) ≤ 0.5 mg/m ² day.

In the experimental example of the present invention, an experiment was performed using a single line laser beam. However, in the case of deposition of a large-area thin film, a multi-line laser beam may be applied for rapid deposition. In this case, it is preferable to increase the output of the laser beam so that each laser beam constituting the multi-line laser beam can have the same power as the single line laser beam.

Although the technical idea of the present invention described above has been described in detail in a preferred embodiment, it should be noted that the embodiment is for the purpose of explanation and not for the limitation thereof. In addition, those of ordinary skill in the technical field of the present invention will understand that various embodiments are possible within the scope of the technical idea of the present invention. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

1: Laser Assisted Plasma Enhanced Chemical Vapor Deposition (LAPECVD)
100: laser generating unit 200: optical system unit
201: reflective mirror
210: laser irradiation drive unit
220: multifocal optical system
230: multi-split lens
231: lens holder
L: laser
ML: Multiline laser
LP: laser irradiation point
300: chamber part
310: chamber
320: reaction material supply unit
330: shower head (cathode)
340: plasma energy generation unit
350: Susceptor (anode) stage
360: laser port
S: substrate

Claims (17)

Laser generator;
An optical system unit for adjusting the focus and path of the laser generated by the laser generating unit; And
Including; a chamber unit for performing plasma chemical vapor deposition on a substrate to be deposited with a reactive material by spraying a reactive material on the path of the laser output from the optical system unit,
In the optical system unit, a laser whose focus and path are adjusted is irradiated into the chamber unit from a side direction of the chamber,
The optical system unit comprises a multifocal optical system having a multi-segmenting lens for converting the laser into a multi-line laser by dividing the laser into a plurality of lines at predetermined intervals in a lateral direction of the laser irradiation direction. Plasma chemical vapor deposition device. The method of claim 1, wherein the laser,
Laser plasma chemical vapor deposition apparatus, characterized in that configured to be irradiated into the chamber from both sides of the chamber. The method of claim 1, wherein the laser output from the laser generating unit,
Laser plasma chemical vapor deposition apparatus, characterized in that it has a wavelength in the range of 150 to 20,000 nm. The method of claim 1, wherein the laser output from the laser generating unit,
Laser plasma chemical vapor deposition apparatus, characterized in that it has a power density in the range of 0.001 W / mm ² to 100 W / mm ² on the substrate in the deposition chamber. delete Laser generator;
An optical system unit for adjusting the focus and path of the laser generated by the laser generating unit; And
Including; a chamber unit for performing plasma chemical vapor deposition on a substrate to be deposited with a reactive material by spraying a reactive material on the path of the laser output from the optical system unit,
In the optical system unit, a laser whose focus and path are adjusted is irradiated into the chamber unit from a side direction of the chamber,
The optical system unit selectively moves the laser in a z-axis perpendicular to the laser irradiation direction, a y-axis in the laser irradiation direction, and an x-axis horizontally in the laser irradiation direction to scan the laser into the chamber unit or A laser plasma chemical vapor deposition apparatus comprising: a laser irradiation driving unit that performs vibration scan and irradiation. The method of claim 6, wherein the laser irradiation driving unit,
The laser plasma chemical vapor deposition apparatus, characterized in that configured to vibrate the laser in the x-axis direction during scan irradiation of the laser. The method of claim 6, wherein the laser irradiation driving unit,
The laser plasma chemical vapor deposition apparatus, characterized in that configured to vibrate the laser in a z-axis direction during scan irradiation of the laser. Laser generator;
An optical system unit for adjusting the focus and path of the laser generated by the laser generating unit; And
Including; a chamber unit for performing plasma chemical vapor deposition on a substrate to be deposited with a reactive material by spraying a reactive material on the path of the laser output from the optical system unit,
In the optical system unit, a laser whose focus and path are adjusted is irradiated into the chamber unit from a side direction of the chamber,
The optical system unit has an irradiation area corresponding to an area in which the length of the substrate is divided by a predetermined interval, and is configured to sequentially scan and irradiate the entire length of the substrate for each irradiation area. Chemical vapor deposition device. The method of claim 1, wherein the chamber unit,
chamber;
A reaction material supply unit formed above the chamber to supply a reactant material into the chamber;
A showerhead installed under the reactant supply unit, having a cathode, and spraying the reactant material evenly to the substrate side;
A plasma energy generator for supplying plasma energy to the interior of the chamber to convert the reaction material injected into the chamber into plasma; And
A laser plasma chemical vapor deposition apparatus comprising: a susceptor disposed under the Shawe head to support the substrate and acting as an anode. The method of claim 10, wherein the plasma energy generating unit,
A laser plasma chemical vapor deposition apparatus, characterized in that it is configured to irradiate the reactant material to have a plasma energy density in the range of 0.01 to 10 W/cm ² . In the chemical vapor deposition method using the laser plasma chemical vapor deposition apparatus of claim 1,
A reaction material injection step of injecting a reaction material into the chamber unit through the reaction material supply unit;
Plasmaizing the reactant material into plasma by supplying plasma energy into the chamber through a plasma energy generator; And
And a laser irradiation step of irradiating the laser output from the laser generating unit into the chamber unit from a side direction of the chamber unit to promote a plasma reaction of the reactants supplied into the chamber unit. Characterized by,
The laser irradiation step is a step of dividing the laser into a plurality of lines at predetermined intervals in a lateral direction of the laser irradiation direction by a multi-segment lens provided in the optical system, converting it into a multi-line laser, and irradiating it. Laser plasma chemical vapor deposition method. The method of claim 12, wherein the laser irradiation step,
The laser plasma chemical vapor deposition method, characterized in that the step of irradiating the interior of the chamber from both sides of the chamber part. delete The method of claim 12, wherein the laser irradiated in the laser irradiation step,
Laser plasma chemical vapor deposition method, characterized in that it has a wavelength in the range of 150 nm to 20,000 nm The method of claim 12, wherein the laser irradiated in the laser irradiation step,
Laser plasma chemical vapor deposition method, characterized in that it has a power in the range of 0.001 W / mm ² to 100 W / mm ² on the substrate inside the chamber part. The method of claim 12, wherein the plasmaizing step,
A laser plasma chemical vapor deposition method, characterized in that supplying plasma energy having a plasma energy density in the range of 0.01 to 100 W/cm ² for plasmaizing the reactant.

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