KR20200055611A - 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 using a laser, and more specifically, to a plasma chemical vapor deposition apparatus using a laser to form a high-quality deposition layer even at low temperatures in chemical vapor deposition. One embodiment of the present invention provides a plasma chemical vapor deposition apparatus using a laser, which includes a laser generating unit, an optical system unit adjusting the focus and path of a laser beam generated by the laser generating unit, and a chamber unit spraying a reactant on the path of the laser beam output from the optical system unit to perform plasma chemical vapor deposition on a substrate, which is an object of reactant deposition. The laser beam is projected in a direction parallel to the substrate inside the chamber unit.

Description

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 a method capable of forming a high-quality deposition layer at a low temperature during chemical vapor deposition.

The CVD (chemical vapor deposition) method refers to a chemical vapor deposition method, and uses a principle of depositing a thin film through high temperature decomposition or high temperature chemical reaction on a substrate in a chamber by spraying a gas or liquid of a material to be deposited on the 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 high purity materials.

For this reason, it is currently the most widely used method in semiconductor manufacturing processes and OLED display manufacturing.

Among CVD and CVD methods, laser chemical vapor deposition (LACVD) injects a reactant into a chamber where the substrate is located, and then irradiates a laser to perform a chemical reaction with the substrate to form a thin film by depositing it on the substrate. Is how to do it.

In addition, plasma chemical vapor deposition (PECVD), when the desired pressure and substrate temperature are set by injecting a reactant such as a liquid containing a reaction gas or a reactant required for deposition inside a chamber forming a vacuum, the ultrahigh frequency is applied to the electrode through a power supply. It is a method of forming a thin film by making a reactant into a plasma state by applying, and ionizing the reactant or precursor to deposit a part of the ionized precursor and the reactant in a plasma state on a substrate by physical or chemical reaction.

In order to increase the efficiency of such a 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 Publication No. 2018-0068637 and Korean Patent Registration No. 123782 disclose a chemical vapor deposition apparatus using a laser that forms a thin film on a substrate by irradiating a laser and then plasmaizing it after supplying a reactant. Doing.

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

In addition, in the case of the above-described laser chemical vapor deposition method, the deposition temperature may be lowered, but the deposition rate is slow and the laser is not uniformly irradiated. Alternatively, 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 Republic of Korea Registered Patent No. 1243782

Therefore, in an embodiment of the present invention for solving the above-described problems of the prior art, in performing plasma chemical vapor deposition, by irradiating a laser so that the energy is uniformly dispersed throughout the reactant to improve the reactivity of the reactant chemistry Laser plasma chemical vapor deposition apparatus suitable for thin film deposition of various materials, including organic materials, etc., while lowering the deposition temperature for vapor deposition, improving the deposition rate on the substrate, and also significantly improving the quality of the deposited thin film. And an object thereof.

One embodiment of the present invention for achieving the above object, a laser generator; An optical system unit that controls the focus and path of the laser generated by the laser generation unit; And a chamber unit that performs a plasma chemical vapor deposition on a substrate to which a reactant is deposited by spraying a reactant on a path of a laser output from the optical system unit. It provides a laser plasma chemical vapor deposition apparatus characterized in that it is irradiated into the chamber.

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

The laser output from the laser generation unit 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 generation unit according to an 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 according to an embodiment of the present invention includes a multifocal optical system having a multi-segmentation lens for dividing the laser into a plurality of lines at predetermined intervals in the lateral direction of the laser irradiation direction and converting it into a multi-line laser. Can be configured.

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

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 according to an embodiment of the present invention, the laser has an irradiation area corresponding to an area in which the length of the substrate is divided at predetermined intervals, and is configured to scan and scan the entire length of the substrate for each irradiation area Can be.

The chamber portion according to an embodiment of the present invention, the chamber; A reactant supply unit formed to supply a reactant to the interior of the chamber on the upper portion of the chamber; A shower head installed on the lower portion of the reactant supply unit, having a cathode, and uniformly dispersing the reactant to spray the substrate; A plasma energy generator that supplies plasma energy to the interior of the chamber to plasma the reactants injected into the chamber; And a susceptor disposed to support the substrate under the shower head and serving as an anode.

The plasma energy generating unit according to an embodiment of the present invention may be configured to irradiate a plasma energy density for plasmaizing the reactant in a 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 portion, a reactant supply unit, a shower head, a plasma energy generating unit and a susceptor that is disposed to support the substrate under the shower head to act as an anode. A chemical vapor deposition method using a laser plasma chemical vapor deposition apparatus comprising: a reactant injection step of injecting a reactant into a chamber portion through the reactant supply unit; Plasmaization step of supplying plasma energy to the interior of the chamber through the plasma energy generating unit to plasma the reactant; And a laser irradiation step of irradiating a laser output from the laser generation unit to the interior of the chamber unit at the same time as the plasmaization step to accelerate the plasma reaction of the reactants supplied into the chamber unit. Provided is 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 to the inside of 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 the lateral direction of the laser irradiation direction by a multi-segmentation lens provided in the optical system, thereby converting the laser into a multi-line laser. It may be a step of conversion and investigation.

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, on the substrate in the chamber, may have a power in the range of 0.001 W / cm ² to 100 W / mm ² .

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

The laser plasma chemical vapor deposition apparatus according to the above-described embodiment of the present invention accelerates plasmaization of a reactant by irradiating a laser in a lateral direction of the reactant during plasma chemical vapor deposition, thereby reducing unreacted gas. It provides the effect of depositing a high-quality thin film on a substrate while lowering the chemical vapor deposition temperature.

The laser plasma chemical vapor deposition apparatus according to the above-described embodiment of the present invention further accelerates plasmaization of the reactant by further irradiating lasers in both directions of the reactant during plasma chemical vapor deposition, thereby further reducing unreacted gas. By providing a plasma chemical vapor deposition temperature lowering, while increasing the substrate deposition rate of the reactant, it provides an effect to deposit a more uniform high-quality thin film.

The laser plasma chemical vapor deposition apparatus according to the above-described embodiment of the present invention is capable of depositing thin films of various materials including organic materials and the like by increasing the substrate deposition rate of a reactant while lowering the plasma chemical vapor deposition temperature. It provides an effect that can be performed as.

1 is a partial plan cross-sectional view of a 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 and the optical system 200 and the chamber 300 for irradiating the laser of the laser generator 100 to the interior of the chamber 300. Partial perspective view of the deposition apparatus.
3 is a view showing the configuration in 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 cross-sectional plan view of the chamber portion 300 of FIG. 1 showing bidirectional irradiation of a multi-laser.
7 is a cross-sectional side view cut in a direction crossing the laser ports 350 on both sides of the chamber part 300 of FIG. 1.
8 is a comparison graph of water vapor transmission rate (WVTR) characteristics of a thin film formed by laser plasma chemical vapor deposition (LAPECVD) and prior art plasma chemical vapor deposition (PECVD) according to an embodiment of the present invention.
9 is a plasma plasma chemical vapor deposition (PECVD) of a thin film formed by irradiation 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. 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 A thin film (TF) formed by irradiating in both directions simultaneously from both sides of a laser plasma chemical vapor deposition (LAPECVD) chamber 300 according to an embodiment of the present invention and formed by plasma chemical vapor deposition (PECVD) of the prior art Graph measuring the change in thickness of each thin film (TF).
12 is a photograph of a thin film (TF) formed by irradiating in both directions simultaneously from both sides of a laser plasma chemical vapor deposition (LAPECVD) chamber 300 according to an embodiment of the present invention.
13 is a flow chart showing the processing of the laser plasma chemical vapor deposition method of another embodiment of the present invention.

In the following description of the present invention, when it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

Since the embodiment according to the concept of the present invention can be modified in various ways 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 embodiment according to the concept of the present invention to a specific disclosure form, and it should be understood that the present invention includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

When an element is said to be "connected" or "connected" to another component, it is understood that other components may be directly connected to or connected to the other component, but there may be other components in between. It should be. On the other hand, when a component is said to be "directly connected" or "directly connected" to another component, it should be understood that no other component exists in the middle. Other expressions that describe the relationship between the components, such as "between" and "immediately between" or "neighboring" and "directly neighboring to" should be interpreted as well.

The terms used in this specification are only used 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 this specification, terms such as “include” or “have” are intended to indicate that a feature, number, step, action, component, part, or combination thereof described is present, and one or more other features or numbers. It should be understood that it does not preclude the presence or addition possibilities of, steps, actions, components, parts or combinations thereof.

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

1 is a partial planar cross-sectional 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 generator 100 into the chamber 300 It is a partial perspective view of a laser plasma chemical vapor deposition apparatus showing a connection configuration between the generator 100 and the optical system 200 and the chamber 300.

1, the laser plasma chemical vapor deposition apparatus 1 according to an embodiment of the present invention, after receiving the output laser (L) of the laser generator 100 and the laser generator 100, focus control And a plasma chemical vapor on the substrate by spraying a reactant on the path of the optical system 200 and the laser L output from the optical system 200 to perform the light path adjustment and irradiate the interior of the chamber 300. It is composed of a chamber part 300 for performing deposition, and irradiates a laser in the lateral direction of the plasma-reacted reaction gas inside the chamber part 300 to plasma an unreacted reactant to form a laser plasma chemical vapor. A thin film is laminated on a substrate loaded inside the chamber 300 by performing deposition (LAPECVD: Laser Assisted Plasma Enhanced Chemical Vapor Deposition).

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

In addition, the laser (L) generated by the laser generator 100 may be irradiated by adjusting the power density to have a range of 0.001 W / cm ² to 100 W / mm ² on the substrate inside the chamber. 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 effectively occur. In addition, when the power of the laser L output from the laser unit 10 exceeds 100 W / mm ² , production cost may increase due to an increase in laser cost.

The optical system 200 is composed of a plurality of convex, concave, or fly lenses such as lenses and reflectors for adjusting the path and focus of the laser L, and output from the laser generator 100 The laser L may be configured to irradiate from the lateral direction of the chamber 300 to the interior of the chamber 300. At this time, the optical system 200 may be configured to have a double laser path so that the laser L is simultaneously irradiated into the chamber 300 from both sides of the chamber 300.

The optical system 200 converts and irradiates the laser to a multi-line laser ML having a plurality of laser lines, and is configured to vary the irradiation direction in the vertical horizontal and traveling directions of the multi-line laser ML. It might be.

3 is a view showing the configuration in a multi-focus optical system 220 according to an embodiment of the present invention, Figure 4 is an optical device 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 multi-focus optical system 220, and (c) is multi-divided by the multi-focus optical system 220. Shows the focus (LP) picture of the laser (ML).

As shown in (b) of FIG. 3, the multifocal optical system 220 includes a multi-segmentation lens 230 and a multi-segmentation lens for forming the laser L into a multi-line laser ML having multiple focuses. It comprises a lens holder 231 for fixing the 230. In this case, the multi-division lens 230 may be a fly lens in which lenses having a plurality of focuses are arranged.

The multi-focus optical system 220 having the above-described configuration, as shown in Fig. 3 (a), after receiving the laser (L) output from the laser generating unit 100 through the reflection mirror 201, etc., horizontal to each other It is converted to a multi-line laser (ML) having a plurality of laser lines that proceeds to output. The converted multi-line laser ML is divided into predetermined intervals along the x-axis direction, which is a 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 multiple focus (LP). Accordingly, the laser irradiation area to the reactant is increased in the x-axis direction inside the chamber 300, and the multi-line laser is divided into regions of a width divided by scanning and irradiating the multi-line laser ML in the x-axis direction. (ML) is superimposed to improve the plasmaization efficiency of the reactants.

As shown in FIG. 4, the laser irradiation driving unit 210 is equipped with a single focus optical system (not shown) or the multi-focus optical system 220, and is configured to move the single-focus optical system or multi-focus optical system along the y-axis direction. The y-axis driving unit ym, the x-axis driving unit xm and the y-axis driving unit yn installed below the y-axis driving unit y to move the y-axis driving unit ym in the x-axis direction. It is configured to include a z-axis driving unit (zm) that is installed on the lower portion of the x-axis driving unit (xm) so as to move the x-axis driving unit (xm) in the vertical direction at the same time. At this time, the x-axis is the horizontal direction to the laser (L) or multi-line laser (ML) irradiation direction, the y-axis is the laser (L) or the multi-line laser (ML) irradiation direction, 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 may be selectively moved in the three-axis direction of the x, y, and z axes of the single focus optical system or the multi-focus optical system 220, or the single focus optical system or Adjusting the irradiation direction, scan direction or horizontal-vertical vibration of a single-focus laser irradiated through the multi-focus optical system 220 or a multi-line laser ML divided into multiple lines and irradiated.

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

And, the laser irradiated from both sides of the chamber part 300 is generated in one laser generation part 200 through one laser generation part 100 and two optical system parts 20, unlike the configuration of FIG. 1. The laser may be configured to be divided into two paths and irradiated by two optical system units 200. In this case, the laser is irradiated from both sides of the chamber part 300 in consideration of the loss of the laser energy by air on the optical path through which the laser passes by dividing and irradiating the laser with a larger laser energy. It may be configured to irradiate in both directions so that they overlap with the same or similar intensity to each other.

As described above, when irradiating a laser (L) or a multi-line laser (ML) to the interior of the chamber 300 on both sides of the chamber 300, the laser (L) or 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 part 300 of FIG. 1 will be described.

FIG. 6 is a cross-sectional partial plan view of the chamber part 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 part 300 of FIG. 1. It is a side sectional view.

6 and 7, the chamber part 300 is installed at a lower portion of the reactant supply portion 320 and the reactant supply portion 320 constituting the chamber 310, and has a negative electrode and has a reactant Plasma energy generation unit that supplies high-frequency plasma energy such as a coil formed inside the chamber 310 to plasma the reactant sprayed into the shower head 330 and the chamber 310 by dispersing the spray evenly. 340, a laser (L) or a multi-line laser (ML) of the susceptor 350 and the chamber 310, which are arranged to support the substrate S at the lower portion of the showerhead 330 and serve as an anode, is irradiated. It is configured to include one or a pair of laser ports 360 installed on one side or both sides.

The reactant supply unit 320 is configured to supply a reactant to a space to perform chemical vapor deposition of laser plasma inside the chamber 310. The reactants injected into the chamber 300 are argon (Ar), helium (He), krypton (Kr), xenon (Xe), neon (Ne), silicon hydride (SiH ₄ , Si ₂ H ₄ ) , Nitrogen oxide (N ₂ O), Oxygen (O ₂ ), Nitrogen (N ₂ ), Ammonia (NH ₃ ), Reactive Gas, Trimethylaluminum (TMA), H ₂ O.

The shower head 330 is configured to disperse and spray the reactants so that the reactants flowing therein are uniformly sprayed on the upper portion of the substrate S. Then, the reactant plasmaized is transferred to the substrate S to form a thin film.

The plasma energy generating unit 340 is configured to supply plasma energy to the interior of the chamber 310 by applying a high frequency to a coil or the like configured inside the chamber 310.

The plasma energy supply unit 340 is an RF unit, match, and chamber 310 for forming a high frequency or electric field, etc., for plasmaizing the reactants injected into the chamber 310 in the interior space of the chamber 310 ) May include an antenna or an electrode rod formed inside. At this time, 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 sufficient plasma may not be formed when the plasma energy density is 0.01 W / cm ² or less, and uniformity of the thin film may be reduced by excessive plasma formation when the plasma energy density is 10 W / cm ² or more.

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

The laser port 360 functions as a window that receives a laser L or a multi-line laser ML emitted from the optical system 200 into the chamber 300. To this end, the laser port 350 is provided with at least one air curtain tube on the upper side of the interior, the optical system 200 in the surface where the laser (L) or multi-line laser (ML) of the chamber part 300 is incident It may be configured to include a tubular laser port case mounted to protrude to the, and a laser irradiation window installed in the end opening of the laser port case. At this time, the laser irradiation window may be formed to have a width greater than the width of the target substrate to form a thin film to perform a scan irradiation of a laser (L) or a multi-line laser (ML) for the entire upper region of the substrate. have.

In order to prevent the plasma curtained reactant from being deposited on the irradiation window, the air curtain tube sprays a non-reactive gas such as nitrogen or argon gas onto the irradiation window in a downwardly downward direction, thereby causing the plasmad reactant to flow into the irradiation window. It can be configured to form an air curtain that prevents movement.

The laser plasma chemical vapor deposition apparatus 1 according to an embodiment of the present invention having the above-described configuration is equipped with a substrate S inside the chamber part 300, sprays a reactant, and then supplies plasma energy to supply plasma. In the process of performing chemical vapor deposition, the laser output from the laser generator 100 is converted into a laser (L) or a multi-line laser (ML) with a focus and a path controlled through the optical system 200 to convert the chamber part ( Plasma unreacted reactants are plasmad by irradiating the reactants inside the chamber 310 in the lateral direction of 300 to improve the plasmaization efficiency of the reactants, thereby improving 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) in the irradiation direction by the laser irradiation driving unit 210 of the optical system 200. Irradiation, vibration is performed in the vertical (z-axis) direction, and scan irradiation is performed in the horizontal direction (x-axis), or scan irradiation is performed in the horizontal direction (x-axis) and vibration irradiation in the horizontal direction (x-axis) is performed in parallel. By performing the vibration scan irradiation, the plasmaization efficiency of the reactant can be significantly improved while lowering the plasmaization temperature, thereby providing an effect of significantly improving the efficiency of plasma chemical vapor deposition.

In addition to this, as shown in FIGS. 1 and 6, a uniform laser is applied to the entire reactant by irradiating while scanning the laser L or the multi-line laser ML focused at both sides of the chamber part 300 from side to side. It provides an effect to further improve the plasmaization efficiency of the reactant and the efficiency of plasma chemical vapor deposition by irradiating energy. At this time, when the substrate is large-area, when scanning in a single direction while scanning the laser L or the multi-line laser ML from side to side, the laser energy is different depending on the distance in the chamber due to the absorption of the laser. Uniformity is lost and uniform thin film deposition cannot be performed. Therefore, in a unidirectional irradiation, it is preferable to irradiate the laser in both directions when depositing a thin film on a large area substrate having a size equal to or greater than that in which the uniformity of laser energy in the large area chamber is broken.

<Experimental Example>

8 is a comparison graph of water vapor transmission rate (WVTR) characteristics of a thin film formed by laser plasma chemical vapor deposition (LAPECVD) and prior art 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 applies an optical system for changing the beam size to 75 mW / mm ² , 80 mm x 5 mm of laser power using the conditions in Table 1 below, and an embodiment of the present invention It was performed 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 on a substrate having a thin film thickness of 300 nm among the substrates on which the thin film was deposited under the above-described conditions, and in FIGS. 8 (a), (b) and (c), plasma chemical vapor deposition (PECVD) of the prior art was performed. A graph showing the results of WVTR measurement of substrates having a thin film formed therein, and (d), (e), and (f) are WVTRs of substrates having a thin film formed by laser plasma chemical vapor deposition (LAPECVD) of an embodiment of the present invention. A graph showing the measurement results is shown.

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

9 and 10 are thin films formed by irradiating from one side of the chamber 300 while scanning the 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] It is a graph showing the uniformity of a thin film formed by plasma chemical vapor deposition (PECVD) of the prior art and a picture of the thin film formed by an embodiment of the present invention.

[Table 2]

9 and 10 in the case of laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention, the power 2 W / mm ² , the scan irradiation speed 20 mm / s, the beam size of 5 x 3 mm ² laser chamber A thin film was deposited by irradiating in one direction from one side of the 300, 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 by position after the thin film TF is deposited, the thickness of the thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention is applied to plasma chemical vapor deposition (PECVD) of the prior art. 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 as the distance from the laser port 460 changes to ± 5.5%. This was considered to be due to the fact that the laser energy was absorbed by the reactant and decreased as it moved away from the laser port 460.

11 and 12 are thin film (TF) formed in both directions of the laser plasma chemical vapor deposition (LAPECVD) chamber 300 according to an embodiment of the present invention under the conditions of [Table 2] at the same time in both directions and the prior art Is a graph measuring the change in thickness of each thin film TF formed by plasma chemical vapor deposition (PECVD), and a photograph of the thin film TF formed by an embodiment of the present invention.

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

As a result of measuring the thickness by position after the thin film TF is deposited, the thickness of the thin film formed by laser plasma chemical vapor deposition (LAPECVD) according to an embodiment of the present invention is applied to plasma chemical vapor deposition (PECVD) of the prior art. 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 even if the thickness by position is far from the laser port 460, the change in thickness is uniform at ± 1.4%. there was. This decreases as the laser energy irradiated in one direction is absorbed by the reactant and moves away from the laser port 460, but in the entire area inside the chamber 310, the laser irradiated in the other direction compensates for the reduced energy. It is because the uniformity of laser energy is ensured.

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

As shown in FIG. 13, the above-described raised plasma chemical vapor deposition method performs a reaction material spraying step (S10) of spraying a reactant into the chamber part 300, thereby depositing a substrate S to be deposited. The reactants are injected inside.

Thereafter, a plasmaization step of plasmaizing the reactant by supplying plasma energy such as high frequency through the plasma energy generation unit 370 inside the chamber 300 is performed.

In the case of performing the plasma-forming step, the laser is output from the laser generating unit 100 so as to supply plasma energy such as a high-frequency or electric field, and to be in a horizontal direction with the substrate S inside the chamber unit 300. By irradiating the interior of the chamber portion 300 through the optical system 200 to perform the laser irradiation step (S30) to accelerate the plasma reaction of the reactant, the reactant on the substrate (S) Is deposited by laser plasma chemical vapor deposition.

The laser irradiation step (S30) of the above-described processing process, by the multi-division lens 230 provided in the optical system 200, the laser in a plurality of lines at predetermined intervals in the lateral direction of the laser irradiation direction It may be divided into a multi-line laser (ML) and irradiated.

In another embodiment of the present invention, the laser irradiation step (S30), the laser generator 100 and the optical system 200 is provided with a double, the chamber portion 300 on both sides of the chamber portion 300 ) It may be a step of irradiating the laser inside. At this time, when the laser is irradiated from both sides of the chamber 300, the laser may be controlled to have 1/2 of the power of the laser when irradiating the laser from one side of the chamber 300. .

Another embodiment of the present invention for achieving the above object is to provide 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 desirable to increase the output of the laser beam so that each laser beam constituting a multi-line laser beam has the same power as a single line laser beam.

It should be noted that although the technical spirit of the present invention described above has been described in detail in a preferred embodiment, the above embodiment is for the purpose of explanation and not of limitation. In addition, a person having ordinary knowledge in the technical field of the present invention will understand that various embodiments are possible within the scope of the technical spirit of the present invention. Therefore, the true technical protection scope of the present invention should be defined by the technical spirit of the appended claims.

1: Laser Plasma Enhanced Chemical Vapor Deposition (LAPECVD)
100: laser generator 200: optical system
201: reflective mirror
210: laser irradiation driving unit
220: multifocal optical system
230: multi-split lens
231: lens holder
L: laser
ML: Multi-line laser
LP: laser irradiation point
300: chamber
310: chamber
320: reactant supply unit
330: shower head (cathode)
340: plasma energy generating unit
350: Susceptor (anode) stage
360: laser port
S: Substrate

Claims (17)

Laser generator;
An optical system unit that controls the focus and path of the laser generated by the laser generation unit; And
It includes; a chamber unit for performing plasma chemical vapor deposition on a substrate to which a reactant is deposited by spraying a reactant on a path of a laser output from the optical system;
A laser plasma chemical vapor deposition apparatus characterized in that a laser whose focus and path are adjusted in the optical system unit is irradiated from the lateral direction of the chamber into the chamber unit. The method of claim 1, wherein the laser,
Laser plasma chemical vapor deposition apparatus, characterized in that configured to be irradiated into the chamber portion from both sides of the chamber portion. According to claim 1, 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. According to claim 1, 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. According to claim 1, The optical system unit,
Laser plasma chemical vapor deposition comprising a multifocal optical system having a multi-segmented lens that divides the laser into a plurality of lines at predetermined intervals in a lateral direction of the laser irradiation direction and converts it into a multi-line laser. Device. According to claim 1, The optical system unit,
The laser is selectively moved in the z-axis perpendicular to the laser irradiation direction, the y-axis in the laser irradiation direction, and the x-axis in the horizontal direction in the laser irradiation direction to scan or irradiate the laser into the chamber portion. A laser plasma chemical vapor deposition apparatus comprising a laser irradiation driving unit. The method of claim 6, wherein the laser irradiation driving unit,
Laser plasma chemical vapor deposition apparatus, characterized in that configured to oscillate the laser in the x-axis direction during the scan irradiation of the laser. The method of claim 6, wherein the laser irradiation driving unit,
A laser plasma chemical vapor deposition apparatus characterized in that it is configured to irradiate the laser in the z-axis direction during the scan irradiation of the laser. According to claim 1, The optical system unit,
A laser plasma chemical vapor deposition apparatus characterized in that the laser has an irradiation area corresponding to an area in which the length of the substrate is divided at predetermined intervals, and the entire length of the substrate is sequentially scanned and irradiated for each irradiation area. . The method of claim 1, wherein the chamber portion,
chamber;
A reactant supply unit formed to supply a reactant to the interior of the chamber on the upper portion of the chamber;
A shower head installed on the lower portion of the reactant supply unit, having a cathode, and uniformly dispersing the reactant to spray the substrate;
A plasma energy generator that supplies plasma energy to the interior of the chamber to plasma the reactants injected into the chamber; And
And a susceptor disposed to support the substrate under the showerhead 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 the plasma energy density for plasmaizing the reactant is configured to be irradiated with a range of 0.01 to 10 W / cm ² . In the method of chemical vapor deposition by a laser plasma chemical vapor deposition apparatus including a chamber, a reactant supply unit, a shower head, a plasma energy generating unit, and a susceptor that is disposed to support the substrate under the shower head and acts as an anode. In,
A reactant injection step of spraying a reactant into the chamber portion through the reactant supply unit;
Plasmaization step of supplying plasma energy to the interior of the chamber through the plasma energy generating unit to plasma the reactant; And
And a laser irradiation step of irradiating a laser output from the laser generation unit to the inside of the chamber unit in a lateral direction of the chamber unit to promote a plasma reaction of the reactants supplied into the chamber unit. Characterized by a laser plasma chemical vapor deposition method. The method of claim 12, wherein the laser irradiation step,
Laser plasma chemical vapor deposition method characterized in that the step of irradiating the laser from both sides of the chamber portion to the interior of the chamber portion. The method of claim 12, wherein the laser irradiation step,
Laser plasma chemical vapor deposition, characterized in that the step of dividing the laser into a plurality of lines at predetermined intervals in the lateral direction of the laser irradiation direction by converting the laser into a multi-line laser by the multi-division lens provided in the optical system. Deposition method. 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 having a power in the range of 0.001 W / mm ² to 100 W / mm ² on the substrate inside the chamber portion. The method of claim 12, wherein the plasma forming step,
Laser plasma chemical vapor deposition method, characterized in that for supplying plasma energy having a plasma energy density in the range of 0.01 to 100 W / cm ² to plasma the reactant.

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