KR20230113130A - Plasma polymerized thin film and preparing method thereof - Google Patents

Abstract

The present application relates to a plasma polymer thin film prepared using a first precursor material represented by Formula 1 and a method for manufacturing the same:
[Formula 1]
;
(In Formula 1 above,
R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).

Description

Plasma polymer thin film and its manufacturing method {PLASMA POLYMERIZED THIN FILM AND PREPARING METHOD THEREOF}

The present application relates to plasma polymer thin films and methods of making the same.

One of the critical steps in modern semiconductor fabrication is the formation of metal and dielectric thin films on substrates by chemical reaction of gases. This deposition process is referred to as chemical vapor deposition or chemical vapor deposition (CVD). In a typical thermal CVD process, a reactive gas is provided to the surface of a substrate, where a heat-induced chemical reaction occurs to form a desired thin film. The thermal CVD process is performed at a high temperature, and the high temperature may damage the structure of a device having a layer formed on a substrate. One of the methods capable of solving this problem, that is, depositing metal and dielectric thin films at a relatively low temperature, is a plasma enhanced CVD method (PECVD).

Plasma-enhanced CVD methods apply radio frequency (RF) energy to a reaction region to promote excitation and/or dissociation of reactive gases, thereby generating a plasma of highly reactive species. Due to the high reactivity of these species, the energy required for the chemical reaction to occur is reduced, and thus the temperature required for thin film formation can be lowered in the plasma enhanced CVD process. The introduction of these devices and methods often enables manufacturing processes that can significantly reduce the size of semiconductor devices.

On the other hand, silicon dioxide (SiO ₂ ) or silicon oxyfluoride (SiOF), which has been mainly used as an interlayer insulating film so far, has high resistance capacitance and signal delay when manufacturing ultra-high integrated circuits of 0.5 μm or less. There are problems such as capacitance delay; RC delay). Therefore, in order to reduce the resistance capacitance signal delay (RC delay) of the multilayer metal film used in the integrated circuit of the semiconductor device, research on forming the interlayer insulating film used in the metal wiring with a material having a low dielectric constant (relative dielectric constant k < 4.0) has been conducted. It's been active lately. Such a low-k thin film may be formed of an inorganic material, such as a SiCOH film mixed with Si, O, C, H, or the like, and an amorphous carbon (aC:F) film doped with fluorine, or an organic material including carbon (C).

Low-dielectric materials currently being considered as substitutes for SiO ₂ include BCB (benzocyclobutene), SILK (supplier: Dow Chemical), and FLARE (fluorinated poly (arylene ether)), which are mainly used for spin coating. Allied Signals), organic polymers such as polyimide, black diamond formed by chemical vapor deposition (Supplier: Applied Materials), Coral (Supplier: Novellus), and xerogel ( There is a porous thin film material such as xerogel or airgel.

Here, since a material having a low dielectric constant formed by a method of spin casting in which spin coating is cured after curing, pores having a size of several nanometers are formed in the thin film, the thin film density is reduced to form a dielectric having a low dielectric constant. In general, the organic polymers deposited by spin coating have a generally low dielectric constant and excellent flatness, but are unsuitable for semiconductor applications because their thermal stability is poor because their heat resistance limit temperature is lower than 450 ° C. Since the size is large and it is not uniformly distributed in the thin film, the mechanical strength of the thin film is low, resulting in various difficulties in device manufacturing. In addition, there are problems such as poor adhesion to upper and lower wiring materials, high stress due to thermal curing peculiar to organic polymer thin films, and reduced reliability of the device due to a change in dielectric constant due to adsorption of ambient moisture.

Korean Patent Registration Nos. 10-1506801 and 10-2138102, which are the background technology of the present application, relate to a low-k plasma polymer thin film and a manufacturing method thereof. The above patent discloses a low-k plasma polymer thin film and a method for manufacturing the low-k plasma polymer thin film manufactured using cross-shaped and H-shaped organic/inorganic precursor materials, respectively, but the deposition rate of the thin film is low and the low dielectric constant value changes after plasma exposure. Due to the existence of limitations, it was difficult to maintain a satisfactory dielectric constant value. Since the low-k thin film is unavoidably exposed to plasma during a subsequent process in a semiconductor process, the range of characteristic change after plasma exposure must be small.

Therefore, the inventors of the present application have achieved an improved deposition rate compared to the prior art by manufacturing a plasma polymer thin film using a new T-type organic/inorganic precursor material, and the conventional plasma polymer has a low density and low carbon ratio in subsequent processes. Although a change in properties may occur after exposure to plasma, the plasma polymer thin film of the present invention shows little change in properties after exposure to plasma due to an appropriate carbon content and density.

The present application is to solve the problems of the prior art, and aims to provide a plasma polymer thin film and a manufacturing method thereof.

However, the technical problems to be achieved by the embodiments of the present application are not limited to the technical problems as described above, and other technical problems may exist.

As a technical means for achieving the above technical problem, a first aspect of the present application provides a plasma polymer thin film prepared using a first precursor material represented by the following formula (1):

[Formula 1]

(In Formula 1 above,

R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).

According to one embodiment of the present application, it may be prepared by using a second precursor material, which is a hydrocarbon in a liquid state at 25° C. and 1 atm, together with the first precursor material, but is not limited thereto.

According to one embodiment of the present application, the second precursor material may include a C ₆ -C ₁₂ alkane, alkene, cycloalkane or cycloalkene, but is limited thereto. it is not going to be

According to one embodiment of the present application, the second precursor material may include cyclohexane, but is not limited thereto.

According to one embodiment of the present application, the first precursor material may have a T-shaped structure, but is not limited thereto.

According to one embodiment of the present application, the plasma polymer thin film may be manufactured using a plasma enhanced CVD method (PECVD), but is not limited thereto.

A second aspect of the present application provides a method for producing a plasma polymer thin film, in which a plasma polymerized thin film is deposited on a substrate using a first precursor material represented by Formula 1 below:

[Formula 1]

(In Formula 1 above,

R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).

According to one embodiment of the present application, the step of depositing the plasma-polymerized thin film on a substrate is a plasma-polymerized second precursor material, which is a hydrocarbon in a liquid state at 25 ° C. and 1 atm, together with the first precursor material. It may be to deposit a thin film on a substrate, but is not limited thereto.

According to one embodiment of the present application, the second precursor material may include a C ₆ -C ₁₂ alkane, alkene, cycloalkane or cycloalkene, but is limited thereto. it is not going to be

According to one embodiment of the present application, the second precursor material may include cyclohexane, but is not limited thereto.

According to one embodiment of the present application, it may be to further include the step of post-processing the thin film deposited on the substrate, but is not limited thereto.

According to one embodiment of the present application, the post-treatment is performed by a process selected from the group consisting of inductively coupled plasma (ICP) treatment, rapid thermal annealing (RTA), and combinations thereof. It may be, but is not limited thereto.

According to one embodiment of the present application, depositing the plasma-polymerized thin film on a substrate may include evaporating the first precursor material and the second precursor material in a bubbler; discharging the evaporated precursor material from the bubbler and introducing it into a plasma deposition reactor; And forming a plasma-polymerized thin film on a substrate in the reactor using the plasma of the reactor; may include, but is not limited thereto.

According to one embodiment of the present application, the reactor may include a carrier gas selected from the group consisting of argon (Ar), helium (He), neon (Ne), and combinations thereof, but is not limited thereto.

According to one embodiment of the present application, the carrier gas pressure of the reactor may be 1×10 ^-1 Torr to 100×10 ^-1 Torr, but is not limited thereto.

According to one embodiment of the present application, the temperature of the substrate in the reactor may be 20 °C to 50 °C, but is not limited thereto.

According to one embodiment of the present application, the power supplied to the reactor may be 10 W to 90 W, but is not limited thereto.

A third aspect of the present application provides a stem cell culture substrate comprising a plasma polymer thin film according to the first aspect of the present application.

According to one embodiment of the present application, the stem cells may have a spheroid shape, but are not limited thereto.

The above-described problem solving means are merely exemplary and should not be construed as intended to limit the present disclosure. In addition to the exemplary embodiments described above, additional embodiments may exist in the drawings and detailed description of the invention.

According to the above-mentioned problem solving means of the present application, the plasma polymer thin film of the present application satisfies the mechanical strength required in the existing semiconductor process by using a precursor material having a T-shaped structure structurally different from the precursor material used in the conventional plasma polymer. However, it is possible to manufacture a plasma polymer thin film having a lower dielectric constant value.

In addition, the plasma polymer thin film according to the present disclosure has a small change in characteristics after plasma exposure due to an appropriate carbon content and density, and thus may have characteristics more suitable for use in a semiconductor process than conventional thin films.

The plasma polymer thin film according to the present invention is thermally stable and has a very low dielectric constant, so it can replace the dielectric used in the metal multilayer wiring of the semiconductor device, and the resistance capacitance signal delay that increases as the metal multilayer wiring is refined ( Resistance Capacitance delay; RC delay) can be improved.

In particular, the plasma polymer thin film of the present disclosure can be directly applied to a metal multilayer wiring process by reducing a dielectric constant while maintaining characteristics required in a semiconductor process, and can improve the resistance capacitance signal delay (RC delay) described above.

However, the effects obtainable herein are not limited to the effects described above, and other effects may exist.

1 is a schematic diagram of a plasma enhanced chemical vapor deposition (CVD) apparatus used to fabricate a plasma polymer thin film according to an embodiment of the present disclosure.
2 is a schematic diagram of a rapid thermal annealing (RTA) apparatus used to fabricate a plasma polymer thin film according to an embodiment of the present disclosure.
3 is a graph showing relative dielectric constant values of a plasma polymer thin film deposited using a first precursor material prepared according to an embodiment of the present disclosure.
4 is a graph of the hardness of a plasma polymer thin film deposited using a first precursor material prepared according to an embodiment of the present disclosure.
5 is a graph of modulus of elasticity (Modulus) of a plasma polymer thin film deposited using a first precursor material prepared according to an embodiment of the present disclosure.
6 is a graph showing the chemical structure obtained by Fourier infrared spectroscopy in a plasma polymer thin film deposited using a first precursor material prepared according to an embodiment of the present disclosure.
7 is a graph showing deposition rates of plasma polymer thin films manufactured according to an example and a comparative example of the present application.
8 is a graph showing relative dielectric constant values of plasma polymer thin films prepared according to one embodiment and a comparative example of the present application.
9 is a graph showing relative dielectric constant values before and after heat treatment of plasma polymer thin films prepared according to an example and a comparative example of the present disclosure.
10 is a graph comparing the strength of plasma polymer thin films prepared according to one embodiment and a comparative example of the present application.
11 is a graph comparing elastic moduli of plasma polymer thin films prepared according to an example and a comparative example of the present disclosure.
12 is a graph showing dielectric constant change values before and after plasma exposure of plasma polymer thin films prepared according to an embodiment and a comparative example of the present disclosure.
13 is a graph showing dielectric constant values according to elastic modulus and carbon ratio of plasma polymer thin films prepared according to an embodiment and a comparative example of the present disclosure.
14 is a result of culturing cells in a plasma polymer thin film according to an embodiment of the present application.

Hereinafter, embodiments of the present application will be described in detail so that those skilled in the art can easily practice with reference to the accompanying drawings. However, the present disclosure may be implemented in many different forms and is not limited to the embodiments described herein. And in order to clearly describe the present application in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a part is said to be "connected" to another part, this includes not only the case of being "directly connected" but also the case of being "electrically connected" with another element in between. do.

Throughout the present specification, when a member is referred to as being “on,” “above,” “on top of,” “below,” “below,” or “below” another member, this means that a member is located in relation to another member. This includes not only the case of contact but also the case of another member between the two members.

Throughout the present specification, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used at or approximating that number when manufacturing and material tolerances inherent in the stated meaning are given, and are intended to assist in the understanding of this disclosure. Accurate or absolute figures are used to prevent undue exploitation by unscrupulous infringers of the stated disclosure. In addition, throughout the present specification, “steps of” or “steps of” do not mean “steps for”.

Throughout the present specification, the term "combination thereof" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It means including one or more selected from the group consisting of.

Throughout this specification, reference to "A and/or B" means "A or B, or A and B".

Hereinafter, the plasma polymer thin film of the present application and its manufacturing method will be described in detail with reference to embodiments and examples and drawings. However, the present application is not limited to these embodiments and examples and drawings.

As a technical means for achieving the above technical problem, a first aspect of the present application provides a plasma polymer thin film prepared using a first precursor material represented by the following formula (1):

[Formula 1]

.

(In Formula 1 above,

R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).

For example, the first precursor may be a compound represented by Formula 2 below, but is not limited thereto:

[Formula 2]

.

The plasma polymer thin film of the present application has mechanical strength required in the conventional semiconductor process by forming nanopores inside the plasma polymer thin film using a first precursor material having a T-shaped structure structurally different from the precursor material used in conventional plasma polymers. It is possible to form a plasma polymer thin film having a lower dielectric constant value while satisfying . For example, a plasma polymer thin film having the dielectric constant value (k) of less than 4.0 may be formed, but is not limited thereto.

Furthermore, the plasma polymer thin film according to the present invention is thermally stable using the first precursor material and has a very low dielectric constant, so it can replace the dielectric used in the metal multilayer wiring of the semiconductor device, and the metal multilayer wiring Resistance capacitance delay (RC delay), which increases with miniaturization, can be improved.

In addition, the plasma polymer thin film according to the present disclosure has a small change in characteristics after plasma exposure due to an appropriate carbon content and density, and thus may have characteristics more suitable for use in a semiconductor process than conventional thin films.

According to one embodiment of the present application, it may be prepared by using a second precursor material, which is a hydrocarbon in a liquid state at 25° C. and 1 atm, together with the first precursor material, but is not limited thereto. Meanwhile, the plasma polymer thin film may be manufactured using only the first precursor material without the second precursor material.

The second precursor material may be a hydrocarbon in a liquid state at 25° C. and 1 atm. When the second precursor material is a hydrocarbon, it can exhibit good bonding strength with the first precursor material, is easy to form a plasma polymer thin film, and furthermore, has a large number of CH _x bond structures to improve the mechanical strength and elasticity of the thin film. can be advantageous Furthermore, the second precursor material is particularly advantageous in that it is in a liquid state in a standard state (25° C. and 1 atm) as described above to be applied to a bubbler of a plasma-enhanced CVD (PECVD) device to be described later. In general, a substance in a liquid state in a standard state is easier to apply to a bubbler, has excellent thin film deposition stability than a solid state, can store a larger amount than a gaseous state, and furthermore plays a role as a bubbler (evaporating the precursor) Hydrocarbons in the phase liquid state may be preferred.

According to one embodiment of the present application, the second precursor material may include a C ₆ -C ₁₂ alkane, alkene, cycloalkane or cycloalkene, but is limited thereto. it is not going to be If the carbon number of the second precursor material is less than C ₆ , it is difficult to be in a liquid state in the standard state and the molecular weight is small, so there may be a problem in that thin film deposition is not easy due to poor mutual bonding with the first precursor material. On the other hand, the carbon number of the second precursor material If is greater than C ₁₂ , it may be in a solid state in a standard state, and it may be difficult to evaporate in a whisk for deposition.

According to one embodiment of the present application, the second precursor material may include cyclohexane, but is not limited thereto.

The first precursor material and the second precursor material may be used in combination at the same time, and as described above, due to their chemical and structural characteristics, mutual bonding can be easily achieved, the stability of the thin film is increased, and a low dielectric constant value is obtained. However, it is possible to provide a plasma polymer thin film having improved mechanical properties.

According to one embodiment of the present application, the first precursor material may have a T-shaped structure, but is not limited thereto. By using the first precursor material having a T-shaped structure, nanopores are formed inside the plasma polymer thin film to satisfy the mechanical strength required in the conventional semiconductor process and have a lower dielectric constant than the plasma polymer thin film manufactured using the conventional precursor. It is possible to form a plasma polymer thin film having a value.

According to one embodiment of the present application, the plasma polymer thin film may be manufactured using a plasma enhanced chemical vapor deposition (hereinafter referred to as 'PECVD'), but is not limited thereto. As described above, the plasma-enhanced CVD method can effectively decompose or excite the first precursor material and the second precursor material by generating plasma of highly reactive species to perform various chemical reactions. For example, they are combined and polymerized. A plasma polymer thin film can be formed. In the case of such a polymer thin film, pores having a size of nanometers or less may be formed, so that it may have relatively excellent mechanical strength while having a low dielectric constant.

When depositing a thin film using the plasma-enhanced CVD method, a thin film having a composition in which the first precursor material and the second precursor material are present at a constant ratio may be formed by adding the first precursor material and the second precursor material at a predetermined ratio. Furthermore, the input amount or input ratio of the first precursor material and the second precursor material may be determined by adjusting the temperature of the bubbler and/or the flow rate of a carrier gas such as argon (Ar). For example, when the first whisker is 40 ° C and the second bubbler is 25 ° C, the flow rate ratio of the first carrier gas: the second carrier gas corresponding to the input ratio of the first precursor material and the second precursor material is 1: 1 A thin film may be deposited at a ratio of 1:5 to 1:5. If the flow rate of the second carrier gas is greater than 5 times that of the first carrier gas, SiO _x in the thin film is significantly reduced, making it difficult to use it as an interlayer insulating film, and the flow rate of the second carrier gas may not reach 1 times that of the first carrier gas. In this case, it may be difficult for the second precursor component to sufficiently flow into the thin film. Furthermore, the plasma polymer thin film may be deposited using a plasma enhanced CVD method and post-treated using RTA. By performing the post-treatment, it was confirmed that the dielectric constant of the plasma polymer thin film according to the present invention can be significantly reduced (see FIG. 9).

A second aspect of the present application provides a method for producing a plasma polymer thin film, in which a plasma polymerized thin film is deposited on a substrate using a first precursor material represented by Formula 1 below:

[Formula 1]

.

(In Formula 1 above,

R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).

With respect to the method for manufacturing a plasma polymer thin film according to the second aspect of the present application, detailed descriptions of parts overlapping with the first aspect of the present application have been omitted, but even if the description is omitted, the contents described in the first aspect of the present application The same can be applied to the second aspect.

The first precursor may be represented by Formula 2 below, but is not limited thereto:

[Formula 2]

.

Preferably, the first precursor may include tris(trimethylsiloxy)silane.

The plasma polymer thin film manufactured according to the above manufacturing method uses a first precursor material having a T-shaped structure structurally different from the precursor material used in the conventional plasma polymer film, and nanopores are formed inside the plasma polymer thin film when the thin film is manufactured. It is possible to form a plasma polymer thin film having a lower dielectric constant value while satisfying the mechanical strength required in the existing semiconductor process.

Furthermore, the plasma polymer thin film manufactured according to the manufacturing method can replace the dielectric used in the metal multilayer wiring of the semiconductor device due to the characteristics of being thermally stable and having a very low dielectric constant using the first precursor material, Resistance capacitance signal delay (RC delay), which increases according to miniaturization of the metal multilayer wiring, can be improved.

In addition, the plasma polymer thin film according to the present disclosure has a small change in characteristics after plasma exposure due to an appropriate carbon content and density, and thus may have characteristics more suitable for use in a semiconductor process than conventional thin films.

According to one embodiment of the present application, the step of depositing the plasma-polymerized thin film on a substrate is a plasma-polymerized second precursor material, which is a hydrocarbon in a liquid state at 25 ° C. and 1 atm, together with the first precursor material. It may be to deposit a thin film on a substrate, but is not limited thereto. Meanwhile, the plasma polymer thin film may be manufactured using only the first precursor material without the second precursor material.

The second precursor material may be a hydrocarbon in a liquid state at 25° C. and 1 atm. The fact that the second precursor material is hydrocarbon can exhibit good bonding strength with the first precursor material, is easy to form a plasma polymer thin film, and is advantageous in that it can improve the mechanical strength and elasticity of the thin film due to the existence of a large number of CH _x bonding structures. can Furthermore, it is advantageous to apply the second precursor material to a bubbler of a plasma-enhanced CVD (PECVD) device to be described later in that it is in a liquid state in a standard state (25° C. and 1 atm) as described above. In general, a substance in a liquid state in a standard state is easier to apply to a bubbler, has excellent thin film deposition stability than a solid state, can store a larger amount than a gaseous state, and furthermore plays a role as a bubbler (evaporating the precursor) Hydrocarbons in the phase liquid state may be preferred.

According to one embodiment of the present application, the second precursor material may include a C ₆ -C ₁₂ alkane, alkene, cycloalkane or cycloalkene, but is limited thereto. it is not going to be If the carbon number of the second precursor material is less than C ₆ , it is difficult to be in a liquid state in the standard state and the molecular weight is small, so there may be a problem in that thin film deposition is not easy due to poor mutual bonding with the first precursor material. On the other hand, the carbon number of the second precursor material If is greater than C ₁₂ , it may be in a solid state in a standard state, and it may be difficult to evaporate in a whisk for deposition.

According to one embodiment of the present application, the second precursor material may include cyclohexane, but is not limited thereto.

The first precursor material and the second precursor material may be used in combination at the same time, and as described above, due to their chemical and structural characteristics, mutual bonding can be easily achieved and the stability of the thin film is increased, while having a low dielectric constant value. A plasma polymer thin film with improved mechanical properties can be provided.

According to one embodiment of the present application, it may be to further include the step of post-processing the thin film deposited on the substrate, but is not limited thereto.

According to one embodiment of the present application, the post-treatment is inductively coupled plasma (hereinafter referred to as 'ICP') treatment, rapid thermal annealing (hereinafter referred to as 'RTA'), and combinations thereof. It may be performed by a process selected from the group consisting of, but is not limited thereto. A method of lowering the dielectric constant by forming pores inside the dielectric through the post-processing may also be used to improve the dielectric constant. In this case, since the T-type Si-O bond of the first precursor is stronger than other bonds, a solid polymer thin film may be formed using the first precursor material. The post-processing step may not be performed, or may be performed using one or both of the two processing methods.

Hereinafter, a method for manufacturing a plasma polymer thin film according to an embodiment of the present invention will be described in more detail with reference to the accompanying drawings.

1 is a schematic diagram of a plasma enhanced chemical vapor deposition (CVD, hereinafter referred to as 'PECVD') apparatus used to manufacture a plasma polymer thin film according to an embodiment of the present invention.

As shown in FIG. 1, the PECVD apparatus used to manufacture a plasma polymer thin film according to an embodiment of the present invention includes first and second carrier gas storage units 10 containing a carrier gas such as argon (Ar). 11) and first and second flow controllers 20 and 21 that control the number of moles of gas passing through, and first and second bubblers 30 and 31 containing solid or liquid precursors and a reactor 40 defining a constant reaction region. The carrier gas reservoirs 10 and 11 , the flow controllers 20 and 21 , the whisks 30 and 31 and the reactor 40 are connected via a transport tube 50 . The reactor 40 includes an RF electrode 41 located under the substrate 1, an ICP RF coil 42 located above the reactor 40, and a shower head having a plurality of openings to uniformly introduce gas ( 43). An exhaust system is provided at the bottom of the reactor 40 to discharge various materials remaining inside the reactor 40 to the outside during the deposition reaction or after the reaction is completed.

According to the above, a method of depositing a thin film using a PECVD apparatus is as follows.

According to one embodiment of the present application, depositing the plasma-polymerized thin film on a substrate may include evaporating the first precursor material and the second precursor material in a bubbler; conveying the evaporated precursor material from the bubbler and introducing it into a plasma deposition reactor; and forming a plasma-polymerized thin film on a substrate in the reactor using the plasma of the reactor, but is not limited thereto.

Each of the first precursor material and the second precursor material are contained in the first and second whiskers 30 and 31, and the first and second whiskers 30 and 31 are heated to a temperature sufficient to evaporate each precursor material. heat up Here, it does not matter which of the two whisks 30 and 31 the precursor material is contained in, but the heating temperature of each whisk may be adjusted according to the type of precursor contained in the whisk.

Each of the first and second carrier gas storage units 10 and 11 may contain argon (Ar), helium (He), neon (Ne), or a combination thereof as a carrier gas, and the first and second flow rates It flows through the transport tube 50 by the regulators 20 and 21. The carrier gas moving along the transport pipe 50 flows into the precursor solution of the whisks 30 and 31 through the whisk inlet pipe, generates bubbles, carries the vapor phase precursor, and returns to the transport pipe 50 through the bubbler discharge pipe. Enter. In this case, the ratio of the first and second precursor materials introduced into the reactor 40 may be adjusted by adjusting the flow rates of the first and second carrier gases.

More specifically, when the first bubbler is 40 ° C. and the second bubbler is 25 ° C., the flow rate of the first carrier gas: the second carrier gas is 1: 1 to 1: 5, and the first and second precursor materials It may be introduced into the reactor, but is not particularly limited thereto. The carrier gas and the evaporated precursor passing through the bubblers 30 and 31 and flowing along the transport pipe 50 are sprayed through the shower head 43 of the reactor 40. At this time, the RF electrode 41 is connected to the shower head 43 ) activates the injected carrier gas and precursor. After spraying through the showerhead 43 of the reactor 40, the activated precursor is deposited on the substrate 1 to become a thin film. After the deposition reaction is completed, the remaining gas is discharged to the outside by an exhaust system provided at the bottom of the reactor 40 .

According to one embodiment of the present application, the reactor may include a carrier gas selected from the group consisting of argon (Ar), helium (he), neon (Ne), and combinations thereof, but is not limited thereto. Preferably, the reactor may contain argon as a carrier gas.

According to one embodiment of the present application, the carrier gas pressure of the reactor may be 1×10 ^-1 Torr to 100×10 ^-1 Torr, but is not limited thereto.

According to one embodiment of the present application, the temperature of the substrate in the reactor may be 20 °C to 50 °C, but is not limited thereto. If the temperature of the substrate is out of this range, it is difficult to form a thin film with appropriate properties. When the temperature of the substrate is 200° C., the deposition rate of the thin film tends to decrease, and furthermore, a higher substrate temperature may inhibit CH _x formation in the thin film and cause the formation of SiO ₂ .

According to one embodiment of the present application, the power supplied to the reactor may be 10 W to 90 W, but is not limited thereto. If the power is higher or lower than this, there may be a problem in that a thin film having a low dielectric constant with desired properties is not formed.

The pressure of the carrier gas, the temperature of the substrate 1, the supply power, etc. are for activating the precursor material to form plasma in an optimal range that can be deposited on the substrate 1, depending on the type of precursor material. Those skilled in the art can appropriately adjust.

Figure 2 is a schematic diagram of an RTA apparatus used to manufacture a plasma polymer thin film according to an embodiment of the present application.

The RTA device is used to activate electrons during heat treatment of specimens and semiconductor device processing, and to change the interface between thin films or between wafers and thin films. In addition, the RTA device is used to transform the state of the grown thin film and reduce loss due to ion implantation. This RTA is implemented with a heated halogen lamp and a hot chuck. Unlike a furnace, RTA has a short process duration, so it is also called RTP (Rapid Thermal Process). Post-processing may be performed on the plasma-deposited thin film in the previous step using such a heat treatment apparatus.

The inside of the RTA device is surrounded by a plurality of halogen lamps positioned around it, and the lamps generate heat while emitting orange light. This RTA device can heat-treat the plasma-deposited thin film and the substrate 1 on which it is placed at 300°C to 600°C. At this time, if the temperature during the post-treatment is less than 300 ° C, the properties of the initially deposited thin film do not change, and if the temperature exceeds 600 ° C, the structure of the thin film is changed from a thin film with a low dielectric constant to a SiO ₂ thin film. There may be a problem. More preferably, it is preferable to rapidly increase the temperature from the initial temperature to the above temperature within 5 minutes and perform the heat treatment for 1 to 5 minutes in that the thin film structure can be effectively changed. RTA post-treatment may be performed under a pressure of 1×10 ⁻¹ Torr to 100×10 ⁻¹ Torr using nitrogen gas.

A third aspect of the present application provides a stem cell culture substrate comprising a plasma polymer thin film according to the first aspect of the present application.

With respect to the stem cell culture substrate according to the third aspect of the present application, detailed descriptions of parts overlapping with the first and/or second aspects of the present application are omitted, but even if the description is omitted, the first aspect and/or the present application Alternatively, the content described in the second aspect may be equally applied to the third aspect of the present application.

According to one embodiment of the present application, the stem cells may have a spheroid shape, but are not limited thereto.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

[Example] Preparation of plasma polymer thin film (ppNP)

Using the PECVD apparatus shown in FIG. 1, after placing a silicon wafer on the RF electrode 41 in the reactor 40 and making a vacuum in the 10 ^-2 Torr region, tris (trimethylsiloxy) as the first precursor material ) Silane (tris(trimethylsiloxy)silane; NP) was put into the first bubbler 30 and heated to 65° C. to vaporize the precursor solution. As a carrier gas, 99.999% ultra-high purity argon (Ar) gas was used. The argon gas supplied and sprayed the first precursor material to the showerhead 43 of the reactor 40 through the transfer pipe 50 through the bubbler 30 and deposited the first precursor material on the substrate 1 by plasma. At this time, AC power of 13.56 Hz and 90 W or less was used to generate the plasma, and plasma polymerization was performed at a pressure of 1.0 Torr or less and a temperature of 200 ° C or less. The plasma polymer thin film thus deposited will be referred to as 'ppNP'.

Furthermore, in the preparation of the plasma polymer, cyclohexane (hereinafter referred to as 'CHex') was selected as a second precursor material and copolymerization was performed through the above preparation method. This copolymerized plasma polymer thin film will be referred to as 'ppNP:CHex'.

The ppNP thin film was post-processed using the RTA apparatus shown in FIG. 2 . A ppNP thin film was put on the chuck, and heat was generated by 12 halogen lamps surrounding the ppNP thin film, and the ppNP thin film was heat-treated at 500° C. for 5 minutes in a nitrogen atmosphere. The nitrogen gas pressure was 1.0 Torr.

[Comparative Example 1] Preparation of plasma polymer thin film (ppTTMSS)

It was prepared in the same manner as in Example, but tetrakis(trimethylsilyloxy)silane (hereinafter referred to as TTMSS) was used as the first precursor material.

Specifically, Comparative Example 1 is a plasma polymer thin film prepared using a cross-shaped precursor material disclosed in Korean Patent Registration No. 10-1506801.

[Comparative Example 2] Preparation of plasma polymer thin film (ppOMBTSTS)

It was prepared in the same manner as in Example, but as a first precursor material, 1,1,1,3,5,7,7,7-octamethyl-3,5-bis (trimethylsiloxy) tetrasiloxane (1,1, 1,3,5,7,7,7-Octamethyl-3,5-bis(trimethylsiloxy)tetrasiloxane (hereinafter referred to as OMBTSTS) was used.

Specifically, Comparative Example 2 is a plasma polymer thin film prepared using the H-type precursor material disclosed in Korean Patent Registration No. 10-2138102.

[Experimental Example 1] Characteristic analysis experiment of ppNP

3 is a graph showing relative dielectric constant values of plasma polymer thin films (ppNP thin films) deposited at various power values using a first precursor material prepared according to an embodiment of the present disclosure. According to this, the relative dielectric constant value varied from 1.78 to 3.38 depending on the conditions in which the ppNP thin film was deposited.

4 is a graph of the hardness of a plasma polymer thin film (ppNP thin film) deposited using a first precursor material prepared according to an embodiment of the present disclosure. Referring to FIG. 4, the strength of the ppNP thin film increased from 0.4 GPa to 2.5 GPa as the relative dielectric constant increased.

5 is a graph of modulus of elasticity (Modulus) of a plasma polymer thin film (ppNP thin film) deposited using a first precursor material prepared according to an embodiment of the present disclosure. Referring to FIG. 5 , the elastic modulus of the ppNP thin film increased from 5 GPa to 18 GPa as the relative dielectric constant increased.

6 is a graph showing the chemical structure obtained by Fourier infrared spectroscopy in a plasma polymer thin film deposited using a first precursor material prepared according to an embodiment of the present disclosure. Specifically, it is a graph showing the chemical structure of the ppNP thin film according to applied power. As shown here, it can be seen that the ppNP thin film basically has a Si-O-Si bonding structure and a Si-(CH ₃ ) _x bonding structure. In particular, as the power increased, the CH _x bond structure, the Si-CH ₃ bond structure, and the Si-(CH ₃ ) _x bond structure decreased, while the Si-O-Si bond structure was maintained. The CH _x bonding structure, the Si-CH ₃ bonding structure, and the Si-(CH ₃ ) _x bonding structure can lead to a relatively lower dielectric constant, and the Si-O-Si bonding structure can lead to stronger mechanical strength. there is. Therefore, as shown in FIG. 3, the dielectric constant increases as the plasma power increases, and as the dielectric constant increases as shown in FIGS. 4 and 5, the mechanical strength, that is, the strength and elastic modulus of the thin film are excellent. In addition, by forming Si-CH ₂ -Si and Si-CH ₂ -CH ₂ -Si structures derived from Si-H bonds of the present precursor, mechanical strength superior to carbon bond structures such as Si-CH ₃ was formed.

[Experimental Example 2] Comparative experiment of Example and Comparative Example

7 is a graph showing deposition rates of plasma polymer thin films manufactured according to an example and a comparative example of the present application.

Referring to FIG. 7, at a power of 40 W or more, the thin film according to the embodiment of the present invention made of a T-shaped precursor has a better deposition rate than the thin films of Comparative Examples 1 and 2 made of a cross-shaped and H-shaped precursor You can check.

8 is a graph showing relative dielectric constant values of plasma polymer thin films prepared according to one embodiment and a comparative example of the present application.

Referring to FIG. 8 , it can be seen that the relative dielectric constant increases as the plasma power increases, and it can be confirmed that the change width after plasma exposure is smaller than that of Comparative Examples 1 and 2.

9 is a graph showing relative dielectric constant values before and after heat treatment of plasma polymer thin films prepared according to one embodiment and a comparative example of the present application.

Referring to FIG. 9 , it can be confirmed that the relative dielectric constant value of each thin film decreases after heat treatment.

10 is a graph comparing strengths of plasma polymer thin films prepared according to an example and a comparative example of the present disclosure, and FIG. 11 is a graph comparing elastic moduli of plasma polymer thin films prepared according to an example and a comparative example of the present disclosure. am.

Referring to FIGS. 10 and 11 , it can be confirmed that the strength and modulus of elasticity increase as the plasma power increases, and it can be seen that the increase in the embodiment is greater than that of Comparative Examples 1 and 2.

[Experimental Example 3] Comparative experiment of Example and Comparative Example

12 is a graph showing relative dielectric constant values of plasma polymer thin films prepared according to an embodiment and a comparative example of the present disclosure before and after plasma treatment.

Referring to FIG. 12, the thin film according to the embodiment of the present invention made of a T-shaped precursor has a smaller change in dielectric constant value after plasma exposure than the thin films of Comparative Examples 1 and 2 made of cross-shaped and H-shaped precursors You can check.

[Experimental Example 4] Comparison of characteristics according to carbon ratio

13 is a graph showing dielectric constant values according to elastic modulus and carbon ratio of plasma polymer thin films prepared according to an embodiment and a comparative example of the present disclosure.

Referring to FIG. 13, the thin film has a low dielectric constant value compared to the mechanical strength in the region where the carbon composition ratio of the thin film is 20% to 30%, and in that region, the thin film according to the embodiment of the present invention has the smallest change in dielectric constant value before and after plasma exposure. can confirm that

The plasma polymer thin film is advantageous in forming a low dielectric constant when the carbon ratio exceeds 30%, but the thin film is very brittle and has poor elasticity. On the other hand, a carbon ratio of 20% to 15% or less is advantageous for forming a low dielectric constant value and high elasticity, but there is a problem in that the properties of the thin film change and the degree of damage increases after plasma exposure.

Considering the above, the T-type precursor according to the present invention has a carbon ratio of 20% to 30%, which is less changed even after plasma exposure in the current semiconductor process than the cross-shaped and H-shaped precursors, which are the previous patents of the inventors of the present application. shows the best characteristics.

[Experimental Example 5]

14 is a result of culturing stem cells in a plasma polymer thin film according to an embodiment of the present application.

Referring to FIG. 14, it can be seen that when HeLa cells and human mesenchymal stem (hMSC) cells were cultured, stem cells in the form of spheroids, which were not produced before coating, were generated.

The above description of the present application is for illustrative purposes, and those skilled in the art will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof should be construed as being included in the scope of the present application.

1 board
10, 11 carrier gas storage unit
20, 21 flow regulator
30, 31 Whisk
40 reactor
41 RF electrode
42 ICP RF Coil
43 shower head
50 shipping lines

Claims (19)

A plasma polymer thin film prepared using a first precursor material represented by Formula 1 below:
[Formula 1]
;
(In Formula 1 above,
R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).
According to claim 1,
It is prepared by using a second precursor material, which is a hydrocarbon in a liquid state at 25 ° C. and 1 atm, together with the first precursor material,
Plasma polymer thin film.
According to claim 2,
The second precursor material is a plasma polymer thin film comprising a C ₆ -C ₁₂ alkane, alkene, cycloalkane or cycloalkene.
According to claim 2,
Wherein the second precursor material comprises cyclohexane (cyclohexane), the plasma polymer thin film.
According to claim 1,
Wherein the first precursor material has a T-shaped structure, the plasma polymer thin film.
According to claim 1,
The plasma polymer thin film is produced using a plasma enhanced CVD method (PECVD), the plasma polymer thin film.
Depositing a plasma polymerized thin film on a substrate using a first precursor material represented by Formula 1 below,
Method for producing a plasma polymer thin film:
[Formula 1]
;
(In Formula 1 above,
R ₁ to R ₉ are each independently H or a C ₁ -C ₅ substituted or unsubstituted alkyl group, and when R ₁ to R ₉ are substituted, the substituent is an amino group, a hydroxyl group, a cyano group, a halogen group, a nitro group or a methoxy group).
According to claim 7,
The step of depositing the plasma polymerized thin film on a substrate,
Depositing a plasma polymerized thin film on a substrate by using a second precursor material, which is a hydrocarbon in a liquid state at 25 ° C. and 1 atm, together with the first precursor material,
A method for producing a plasma polymer thin film.
According to claim 8,
The second precursor material comprises a C ₆ -C ₁₂ alkane, alkene, cycloalkane or cycloalkene, a method for producing a plasma polymer thin film.
According to claim 8,
The method of manufacturing a plasma polymer thin film, wherein the second precursor material includes cyclohexane.
According to claim 7,
Method for producing a plasma polymer thin film, further comprising the step of post-processing the thin film deposited on the substrate.
According to claim 11,
The post-treatment is performed by a process selected from the group consisting of inductively coupled plasma (ICP) treatment, rapid thermal annealing (RTA), and combinations thereof,
A method for producing a plasma polymer thin film.
According to claim 7,
The step of depositing the plasma polymerized thin film on a substrate,
evaporating the first precursor material and the second precursor material in a whisk;
conveying the evaporated precursor material from the bubbler and introducing it into a plasma deposition reactor; and
forming a plasma-polymerized thin film on a substrate in the reactor using the plasma of the reactor;
including,
A method for producing a plasma polymer thin film.
According to claim 13,
Wherein the reactor comprises a carrier gas selected from the group consisting of argon (Ar), helium (He), neon (Ne), and combinations thereof.
According to claim 13,
The carrier gas pressure of the reactor is 1 × 10 ^-1 Torr to 100 × 10 ^-1 Torr, a method for producing a plasma polymer thin film.
According to claim 13,
The temperature of the substrate in the reactor is 20 ℃ to 50 ℃, the method of producing a plasma polymer thin film.
According to claim 13,
The power supplied to the reactor is 10 W to 90 W, a method for producing a plasma polymer thin film.
A stem cell culture substrate comprising a plasma polymer thin film according to any one of claims 1 to 6.
According to claim 18,
The stem cells have a spheroid shape,
Stem cell culture substrate.