KR20230152251A - Initiated chemical vapor deposition apparatus for improving uniformity of deposition thin film - Google Patents

Abstract

A chemical vapor deposition (iCVD) device according to an embodiment of the present invention includes a deposition chamber, disposed within the deposition chamber, a plurality of first nozzles at the bottom, supplied through a first gas line, and containing a monomer. An upper showerhead that distributes the first gas uniformly in a plane and discharges it through the first nozzle, is disposed below the upper showerhead, and includes a plurality of second nozzles at the lower part, and the first gas flows in through the first nozzle. A second gas containing an initiator is supplied through the second gas line, and the first gas, the second gas, or a mixed gas containing the first gas and the second gas is uniformly distributed on a plane to form a second gas. 2 A lower showerhead that discharges through a nozzle, an activator disposed below the lower showerhead that activates the initiator discharged through the second nozzle, and a polymer organic thin film is formed through a polymerization reaction of a monomer activated by the activated initiator. Large-area mass production-oriented chemical vapor deposition by enabling uniform deposition of polymer organic thin films on large-area substrates, including a susceptor that supports the substrate being deposited and cools the substrate to induce adsorption of the polymer organic thin films. Provides a device.

Description

Chemical vapor deposition device for improving uniformity of deposited thin films {INITIATED CHEMICAL VAPOR DEPOSITION APPARATUS FOR IMPROVING UNIFORMITY OF DEPOSITION THIN FILM}

The present invention relates to a chemical vapor deposition reactor (iCVD) that enables uniform deposition of polymer organic thin films on a large-area substrate by stably supplying initiators and monomers into a deposition chamber.

The initiated Chemical Vapor Deposition (iCVD) process is a method of depositing a polymer organic thin film using polymerization of activated monomers. The chemical vapor deposition process is a dry process that does not use organic solvents or additives used in the existing spin coating liquid process. It can form high purity and high quality polymer organic thin films, and has recently been in the spotlight in the semiconductor device manufacturing process. there is.

In a typical chemical vapor deposition process, monomers and initiators are first introduced into a vacuum-maintained deposition chamber. The introduced initiator is radicalized or activated by filament heat. The activated initiator activates the monomer introduced into the deposition chamber. The activated monomer is adsorbed to the surface of a substrate or substrate requiring thin film deposition and is deposited as a polymer organic thin film through a polymerization reaction. Methods for improving the quality of the chemical vapor deposition process include optimizing the filament array structure, optimizing vacuum formation and process pressure in the deposition chamber, and enabling the activated monomer to stably lose heat energy to form a uniform polymer organic layer. There is a method for forming a thin film.

In existing chemical vapor deposition equipment, the initiator and monomer are supplied into the deposition chamber in a mixed form. Appropriate film formation uniformity of the polymer organic thin film is secured through control of the flow rate of the mixed initiator and monomer, but there is a problem in that the uniformity is significantly lowered when the substrate area is increased.

An embodiment of the present invention provides a chemical vapor deposition device capable of a large-area deposition process for mass production by significantly improving the film formation uniformity of a polymer organic thin film by specifying the injection location of the initiator and monomer in the deposition chamber.

The problem to be solved by the present invention is not limited to the problem(s) mentioned above, and other problem(s) not mentioned will be clearly understood by those skilled in the art from the description below.

A chemical vapor deposition apparatus according to an embodiment of the present invention includes a deposition chamber; It is disposed in the deposition chamber, includes a plurality of first nozzles at the bottom, is supplied through a first gas line, and distributes a first gas containing a monomer uniformly on a plane and discharges through the first nozzle. Shiki upper shower head; A second gas is disposed below the upper shower head and includes a plurality of second nozzles at the bottom, into which the first gas flows through the first nozzle, and which contains an initiator through a second gas line. a lower showerhead to which the first gas, the second gas, or a mixed gas including the first gas and the second gas is uniformly distributed on a plane and discharged through the second nozzle; an activator disposed below the lower showerhead and activating the initiator discharged through the second nozzle; And a susceptor that supports the substrate on which the polymer organic thin film is deposited through the polymerization reaction of the monomer activated by the activated initiator, and cools the substrate to induce adsorption of the polymer organic thin film. You can.

In the above embodiment, the second gas may include an initiator and a monomer.

In the above embodiment, the first gas and the second gas may be supplied simultaneously or sequentially through the first gas line and the second gas line, respectively.

In the above embodiment, the first gas line is connected to the center of the upper shower head to supply the first gas, and the second gas line is connected to the center of the lower shower head to supply the second gas. .

In the above embodiment, the second gas line may extend through the inside of the first gas line and be connected to the center of the lower showerhead.

In the above embodiment, the upper part of the lower showerhead may be covered with the lower part of the upper showerhead.

In the above embodiment, the plurality of first nozzles may be arranged in a grid shape under the upper shower head, and the plurality of second nozzles may be arranged in a grid shape under the lower shower head.

In the above embodiment, the plurality of first nozzles are arranged in a concentric circle at the lower part of the upper showerhead with the same density decreasing toward the center, and the plurality of second nozzles are arranged in a concentric circle at the lower part of the lower showerhead at the same density. They can be arranged in decreasing density towards the center.

In the above embodiment, the activation unit includes a filament or a plasma electrode, the filament may supply heat energy to activate the initiator, and the plasma electrode may activate the initiator through plasma.

A chemical vapor deposition (iCVD) device according to an embodiment of the present invention includes a deposition chamber; It is disposed in the deposition chamber, includes a plurality of first nozzles at the bottom, is supplied through a first gas line, and distributes a first gas containing a monomer uniformly on a plane and discharges through the first nozzle. Shiki upper shower head; It is disposed below the upper shower head, includes a plurality of second nozzles at the bottom, and is supplied through a second gas line. A second gas containing an initiator is uniformly distributed on a plane to form the second nozzles. a lower shower head that discharges air through; an activator disposed below the lower showerhead and activating the initiator discharged through the second nozzle; And a susceptor that supports the substrate on which the polymer organic thin film is deposited through the polymerization reaction of the monomer activated by the activated initiator, and cools the substrate to induce adsorption of the polymer organic thin film. , the first nozzle may be formed to penetrate from the upper part of the lower showerhead to the lower part.

In the above embodiment, the second gas may include an initiator and a monomer.

In the above embodiment, the first gas and the second gas may be supplied simultaneously or sequentially through the first gas line and the second gas line, respectively.

In the above embodiment, the first gas line is connected to the center of the upper shower head to supply the first gas, and the second gas line is connected to the center of the lower shower head to supply the second gas. .

In the above embodiment, the second gas line may extend through the inside of the first gas line and be connected to the center of the lower showerhead.

In the above embodiment, the plurality of first nozzles may be arranged in a grid shape under the upper shower head, and the plurality of second nozzles may be arranged in a grid shape under the lower shower head.

In the above embodiment, the plurality of first nozzles are arranged in a concentric circle at the lower part of the upper showerhead with the same density decreasing toward the center, and the plurality of second nozzles are arranged in a concentric circle at the lower part of the lower showerhead at the same density. They can be arranged in decreasing density towards the center.

In the above embodiment, the activation unit includes a filament or a plasma electrode, the filament may supply heat energy to activate the initiator, and the plasma electrode may activate the initiator through plasma.

According to an embodiment of the present invention, a double shower head is included in the deposition chamber of the chemical vapor deposition apparatus, and the initiator is injected into the deposition chamber through the lower shower head to smoothly activate the initiator and smoothly form the monomer on the substrate surface. and induces a uniform polymerization reaction to uniformly deposit a polymer organic thin film on a large-area substrate.

1 and 2 are diagrams schematically showing a chemical vapor deposition apparatus according to an embodiment of the present invention.
Figure 3 is a diagram schematically showing an example of a dual showerhead structure of a chemical vapor deposition apparatus according to an embodiment of the present invention.
Figure 4 is a diagram schematically showing the arrangement of nozzles included in the lower part of a showerhead according to an embodiment of the present invention.
Figures 5 and 6 are charts showing the uniformity of the polymer organic thin film deposited by changing the top and bottom injection positions of the initiator and monomer.

The advantages and/or features of the present invention and methods for achieving them will become clear by referring to the embodiments described in detail below in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various different forms, but the present embodiments only serve to ensure that the disclosure of the present invention is complete and are within the scope of common knowledge in the technical field to which the present invention pertains. It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

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

1 and 2 are diagrams schematically showing a chemical vapor deposition apparatus according to an embodiment of the present invention.

Referring to FIG. 1, the chemical vapor deposition apparatus according to an embodiment of the present invention receives a first gas (G1) containing a monomer and a second gas (G2) containing an initiator, respectively, and uniformly distributes them in the deposition chamber. (1) Supports the upper showerhead (2) and lower showerhead (3) that discharge to the inside, the activation part (4) that induces activation of the monomer through activation of the initiator, and the substrate (5) on which the polymer organic thin film is deposited. It includes a susceptor (6).

The deposition chamber (1) uses an upper showerhead (2) and a lower showerhead (3) to induce a polymerization reaction of monomers through an activated initiator so that a polymer organic thin film can be deposited on the substrate (5) requiring deposition. , may include an activation unit (4) and a susceptor (6). The deposition chamber 1 may include a vacuum pump (not shown) to maintain low pressure and low vacuum for smooth deposition of the polymer organic thin film. In addition, when the polymer organic thin film is deposited at atmospheric pressure or higher depending on the type of monomer or initiator, the deposition chamber 1 may include a pressure pump (not shown) to maintain an appropriate pressure. .

The upper showerhead 2 receives and receives the first gas G1 from the outside through the first gas line 21. The first gas (G1) contains a monomer, and may include argon (Ar), nitrogen (N ₂ ), or oxygen (O ₂ ) as a carrier gas to smoothly supply the monomer. The upper showerhead 2 allows the first gas G1 to be uniformly spread and distributed on a plane through the open space inside. The uniformly distributed first gas G1 is discharged downward through a plurality of first nozzles 22 formed at the lower portion. The first nozzle 22 may extend inside the lower showerhead 3 (FIG. 1) or may extend from the top to the bottom of the lower showerhead 3 (FIG. 2). As shown in FIG. 1, the first gas G1 discharged from the upper showerhead 2 may flow into the lower showerhead 3. As shown in FIG. 2, the first gas G1 discharged from the upper showerhead 2 may pass through the lower showerhead and directly reach the activation unit 4. In this case, the first gas (G1) and the second gas (G2) are not mixed in the upper and lower showerheads and can independently reach the activation unit (4).

The lower showerhead 3 receives and receives the second gas G2 from the outside through the second gas line 31. The second gas (G2) contains an initiator, and may include argon (Ar), nitrogen (N ₂ ), or oxygen (O ₂ ) as a carrier gas to smoothly supply the initiator. Additionally, the second gas (G2) may include monomers. The lower showerhead 3 may receive the first gas G1 discharged from the upper showerhead 2. The upper part of the lower showerhead 3 may be covered with the lower part of the upper showerhead 2. In this case, the first gas G1 discharged from the first nozzle 22 remains inside the lower showerhead 3. It is accepted. The lower showerhead 3 allows the first gas (G1), the second gas (G2), or a mixture thereof to be uniformly spread and distributed on a plane through the open space inside. The uniformly distributed first gas (G1), second gas (G2), or a mixture thereof is discharged to the bottom through a plurality of second nozzles 32 formed at the bottom. By supplying the initiator below the position where the monomer is mainly supplied, the activation of the initiator and the polymerization reaction of the monomer can occur uniformly on the plane through smooth supply of the initiator, thereby ensuring high uniformity of the final deposited large-area polymer organic thin film. It can be secured. Large-area substrates on which polymer organic thin films are deposited include all types of inorganic and organic materials, and include substrates of all shapes such as squares and circles, and the size of the substrates ranges from small, such as a 4-inch substrate, to large, several meters in size. Applicable.

The first gas supplied to the upper showerhead 2 and the second gas supplied to the lower showerhead 3 may be supplied simultaneously, sequentially, or may be supplied overlapping with a time difference. The supply order of the first gas and the second gas can be appropriately selected in consideration of the type of monomer and initiator, the type and thickness of the polymer organic thin film to be deposited, etc.

The activation unit 4 is located below the lower showerhead 3 and activates or radicalizes the initiator contained in the second gas or mixed gas. The activation unit 4 may include a filament or a plasma electrode. The filament, like a resistive coil, converts electrical energy into heat energy and activates the initiator by supplying the converted heat energy to the initiator. The plasma electrode activates the initiator through plasma in the form of gas ionized by arc generation. The initiator passes through the activation unit 4 and is activated into an unstable state (meta stable state), and activates the nearby gaseous monomer to be in an unstable state.

The susceptor 6 supports the substrate 5 on which the polymer organic thin film is deposited, and cools the substrate 5 for thin film deposition. The susceptor 6 may include a cooling device using a thermoelectric element or a cooling device using coolant or refrigerant gas for efficient and stable cooling of the substrate 5. The activated monomer descends and reaches the surface of the substrate 5 and is adsorbed, and the cooled substrate 5 absorbs the thermal energy of the monomer and improves adsorption. The monomer activated through the above process is deposited as a polymer organic thin film on the substrate 5 through polymerization and deposition.

Figure 3 is a diagram schematically showing an example of a dual showerhead structure of a chemical vapor deposition apparatus according to an embodiment of the present invention.

The first gas and the second gas may be supplied through the centers of the upper showerhead 2 and the lower showerhead 3, respectively, so that they can be uniformly distributed inside the showerhead. In this case, the first gas line 21 and the second gas line 31 are connected to the upper central portion of the upper shower head 2 and the lower shower head 3, respectively, to supply the first gas (G1) and the second gas (G2). ) can be supplied respectively. When the lower part of the upper showerhead (2) and the upper part of the lower showerhead (3) are integrally connected, the second gas line (31) passes through the center of the upper showerhead (2) and connects the upper part of the lower showerhead (3). can be connected with Referring to FIG. 2, the second gas line 31 extends inside the first gas line 21 at some sections, passes through the center of the upper shower head, and can be connected to the upper part of the center of the lower shower head 3. there is. By inducing uniform radial diffusion of the first gas and the second gas in this way, a more uniform distribution effect can be obtained in the entire plane.

Figure 4 is a diagram schematically showing the arrangement of nozzles included in the lower part of a showerhead according to an embodiment of the present invention.

Referring to FIG. 4, a plurality of first nozzles 22 may be arranged in a lattice shape under the upper showerhead 2. Likewise, a plurality of second nozzles 32 may be arranged in a grid under the lower showerhead 3. However, it is not limited to this, and the distance between the first nozzle 22 and the second nozzle 32 may be arranged non-uniformly in consideration of the size of the substrate, the diffusion speed of the first gas and the second gas, etc. For example, the closer to the center, the greater the separation distance between the first nozzles 22 and the second nozzles 32, that is, they may be arranged at a reduced density. In this case, the densities of the first nozzles 22 and the second nozzles 32 may be arranged the same in a concentric circle.

Figures 5 and 6 are charts showing the uniformity of the polymer organic thin film deposited by changing the top and bottom injection positions of the initiator and monomer.

Tables 1 to 3 below show the results of non-uniformity in the thickness of the polymer organic thin film deposited according to the top and bottom injection positions of the monomer and initiator, the chart for Table 2 is in Figure 5, and the chart for Table 3 is in Figure 6. am. Non-uniformity is a value that quantifies the degree of non-uniformity. It is the deviation of the thicknesses measured at at least 13 points of the thin film deposited at different positions on the plane. The lower the uniformity, the better the uniformity. In Tables 1 to 3, the area of the large-area substrate used for the polymer organic thin film is 50×50 cm2. For comparison, results for a 30×30 cm2 substrate (blue) are also shown in Figures 5 and 6. Tert-butyl peroxide (TBPO) was used as an initiator.

Upper showerhead (first gas): initiator
Lower shower head (second gas): monomer TBPO pressure
(Torr) thin film thickness
(nm) deposition rate
(nm/min) unevenness
(%) 0.74 274.93 4.58 29.1

Upper shower head (first gas): Not injected
Lower showerhead (second gas): initiator, monomer TBPO pressure
(Torr) thin film thickness
(nm) deposition rate
(nm/min) unevenness
(%) 0.375 405.08 6.75 17.1 0.563 296.06 4.93 18.2 0.75 271.48 4.52 16.0 1.0 134.96 2.25 10.4

Upper showerhead (first gas): monomer
Lower showerhead (second gas): initiator TBPO pressure
(Torr) thin film thickness
(nm) deposition rate
(nm/min) unevenness
(%) 0.375 141.1 2.35 13.4 0.56 99.58 1.66 10.5 0.75 55.83 0.93 13.9

The non-uniformity of the polymer organic thin film deposited on a large-area substrate must be less than 15% to be suitable for mass production. Table 1 and Table 2 show that the non-uniformity value exceeds 15%, indicating that inappropriate results may be obtained depending on the pressure of the TBPO. In addition, the case in Table 3 showed the lowest unevenness under the same TBPO pressure conditions (0.74 or 0.75 Torr). In particular, Table 3 showed excellent thin film quality with non-uniformity values of less than 15% in all pressure conditions. These results can be assumed to have a beneficial effect on the thickness uniformity of the polymer organic thin film by supplying the initiator to the lower showerhead of the double showerhead to uniformly induce the activation of the initiator and the polymerization reaction of the monomer. Therefore, by injecting the initiator into the lower showerhead, a large-area chemical vapor deposition device for mass production can be made possible.

Although the specific embodiments according to the present invention have been described so far, it goes without saying that various modifications are possible without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the scope of the patent claims described below as well as equivalents to the claims of this patent.

As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited to the above embodiments, and those skilled in the art can make various modifications and modifications from these descriptions. Transformation is possible. Accordingly, the spirit of the present invention should be understood only by the scope of the claims set forth below, and all equivalent or equivalent modifications thereof shall fall within the scope of the spirit of the present invention.

1: Deposition chamber
2: Upper showerhead
21: First gas line
22: First nozzle
3: Lower showerhead
31: Second gas line
32: Second nozzle
4: Activation unit
5: substrate
6: Susceptor

Claims (17)

In a chemical vapor deposition (iCVD) device,
deposition chamber;
It is disposed in the deposition chamber, includes a plurality of first nozzles at the bottom, is supplied through a first gas line, and distributes a first gas containing a monomer uniformly on a plane and discharges through the first nozzle. Shiki upper shower head;
A second gas is disposed below the upper shower head and includes a plurality of second nozzles at the bottom, into which the first gas flows through the first nozzle, and which contains an initiator through a second gas line. a lower showerhead to which the first gas, the second gas, or a mixed gas including the first gas and the second gas is uniformly distributed on a plane and discharged through the second nozzle;
an activator disposed below the lower showerhead and activating the initiator discharged through the second nozzle; and
A susceptor that supports a substrate on which a polymer organic thin film is deposited through a polymerization reaction of the monomer activated by the activated initiator, and cools the substrate to induce adsorption of the polymer organic thin film. Characterized by a chemical vapor deposition device.
According to paragraph 1,
The second gas is a chemical vapor deposition device characterized in that it contains an initiator and a monomer.
According to paragraph 1,
The chemical vapor deposition device is characterized in that the first gas and the second gas are supplied simultaneously or sequentially through the first gas line and the second gas line, respectively.
According to paragraph 1,
The first gas line is connected to the center of the upper shower head to supply the first gas, and the second gas line is connected to the center of the lower shower head to supply the second gas. Vapor deposition device.
According to paragraph 4,
The second gas line extends through the inside of the first gas line and connects to the center of the lower showerhead.
According to paragraph 1,
A chemical vapor deposition device, characterized in that the upper part of the lower showerhead is covered with the lower part of the upper showerhead.
According to paragraph 1,
The chemical vapor deposition apparatus, wherein the plurality of first nozzles are arranged in a grid shape under the upper shower head, and the plurality of second nozzles are arranged in a grid shape under the lower shower head.
According to paragraph 1,
The plurality of first nozzles are arranged in a concentric circle at the lower part of the upper showerhead with the same density decreasing toward the center, and the plurality of second nozzles are arranged at the lower part of the lower showerhead at the same density in a concentric circle. A chemical vapor deposition device characterized in that it is arranged with a density decreasing toward.
According to paragraph 1,
The activating part includes a filament or a plasma electrode,
The filament supplies heat energy to activate the initiator, and the plasma electrode activates the initiator through plasma.
In a chemical vapor deposition (iCVD) device,
deposition chamber;
It is disposed in the deposition chamber, includes a plurality of first nozzles at the bottom, is supplied through a first gas line, and distributes a first gas containing a monomer uniformly on a plane and discharges through the first nozzle. Shiki upper shower head;
It is disposed below the upper shower head, includes a plurality of second nozzles at the bottom, and is supplied through a second gas line. A second gas containing an initiator is uniformly distributed on a plane to form the second nozzles. a lower shower head that discharges air through;
an activator disposed below the lower showerhead and activating the initiator discharged through the second nozzle; and
A susceptor that supports the substrate on which the polymer organic thin film is deposited through the polymerization reaction of the monomer activated by the activated initiator, and cools the substrate to induce adsorption of the polymer organic thin film,
The first nozzle is a chemical vapor deposition device, characterized in that it is formed by penetrating from the top to the bottom of the lower showerhead.
According to clause 10,
The second gas is a chemical vapor deposition device characterized in that it contains an initiator and a monomer.
According to clause 10,
The chemical vapor deposition device is characterized in that the first gas and the second gas are supplied simultaneously or sequentially through the first gas line and the second gas line, respectively.
According to clause 10,
The first gas line is connected to the center of the upper shower head to supply the first gas, and the second gas line is connected to the center of the lower shower head to supply the second gas. Vapor deposition device.
According to clause 13,
The second gas line extends through the inside of the first gas line and connects to the center of the lower showerhead.
According to clause 10,
The chemical vapor deposition apparatus, wherein the plurality of first nozzles are arranged in a grid shape under the upper shower head, and the plurality of second nozzles are arranged in a grid shape under the lower shower head.
According to clause 10,
The plurality of first nozzles are arranged in a concentric circle at the lower part of the upper showerhead with the same density decreasing toward the center, and the plurality of second nozzles are arranged at the lower part of the lower showerhead at the same density in a concentric circle. A chemical vapor deposition device characterized in that it is arranged with a density decreasing toward.
According to clause 10,
The activating part includes a filament or a plasma electrode,
The filament supplies heat energy to activate the initiator, and the plasma electrode activates the initiator through plasma.