KR101354433B1 - The thin film and method for manufacturing thin film containing fluorine - Google Patents

Abstract

The present invention relates to a fluorine-containing thin film production method and a thin film which control the physical properties of the thin film by using a fluoride to improve physical properties such as corrosion resistance and abrasion resistance according to the environment of use of the product.
To this end, after coating the DLC layer on the surface of the substrate, the surface of the DLC layer is characterized by coating the fluorine layer using a gas of fluoride.
According to the above configuration, the porous structure is formed by the inclusion of fluorine, the surface of the thin film becomes hydrophobic, and the wettability of the surface is reduced, thereby increasing the corrosion resistance. In particular, the friction coefficient is increased by the surface layer serving as a pocket of oil. There is an effect that can be applied to the automotive parts that require improved durability.

Description

Fluorine-containing thin film manufacturing method and thin film {THE THIN FILM AND METHOD FOR MANUFACTURING THIN FILM CONTAINING FLUORINE}

The present invention relates to a method for producing a thin film containing fluorine and a thin film thereof, and more particularly, by controlling the properties of the film by using a fluoride on the surface of the DLC coating layer, according to the environment of use of the product, such as corrosion resistance and wear resistance It relates to a thin film manufacturing method and a thin film containing fluorine to improve the.

In general, DLC (Diamond-Like Carbon) coating is known for the first time developed through the ion implantation technology in the 1970s, and is currently in the spotlight as a protective film due to its high hardness of 40 GPa or more and the high lubricity of 0.2 or less.

DLC is a coating material capable of incorporating hydrogen, Si and various metals according to the manufacturing method while the SP3 structure of the diamond structure and the SP2 structure of graphite are mixed. In other words, the diamond's solid properties and graphite's lubricity at the same time, the application field of DLC coating is applied to parts requiring lubrication and high hardness such as molds, machine parts, automobiles, cutting tools, and so on. It is expected that the scope of use will be extended in the future through the establishment of research and application fields.

In particular, DLC has been evaluated as a material with high industrial potential because of its excellent mechanical properties such as high hardness, wear resistance, lubricity, surface roughness, electrical insulation, chemical stability, and high optical transmittance, and can be deposited at low process temperatures. This has the advantage of high hardness and low coefficient of friction.

However, when DLC is thermally unstable and the environment used is over 500 ℃, DLC loses its properties and becomes a nearly graphite material, and high compression stress and low adhesion to the substrate are disadvantages. Appearing.

On the other hand, the deposition method of the DLC thin film includes an ion deposition method, sputtering method, arc ion plating method, PECVD method, etc. Among the commercially available methods, the coating method using sputtering is mainly used.

In the sputtering process, argon ions or the like are collided with a target to which a negative voltage is applied at high speed to release target atoms, and the thin film is formed on the surface of the base material by supplying them to the base material. The sputtering process is used in the field of semiconductor manufacturing process, coating for improving the wear resistance of various tools, molds, automotive parts, as well as the manufacture of micro devices such as MEMS.

In the case of automobile manufacturers applying the DLC coating layer through the sputtering method, the physical properties of the coating layer vary according to the difference between the ratio of the SP3 and SP2 structures and the hydrogen content.

Looking at the physical properties of the coating layer, the friction coefficient can be reduced to 0.05 or less, the hardness is more than 3000Hv. Currently, the effects obtained through the application of single products have been reported to reduce fuel consumption by 0.8% and reduce fuel costs by 10 billion, which is similar to the cost of using 50kg of aluminum alloy when light weighted. The same effect can be achieved at a level cost.

However, even though the coating characteristics are excellent, both the price and shape of the part to be applied must be satisfied and the price competitiveness must be excellent from the user's point of view. There is a lot of research going on to have both.

In addition, automakers are trying to replace the existing engine oil from GF3 (or A) to GF4 oil (or B), which has been shown to cause problems with DLC durability in GF4 oil. That is, FIG. 1 shows a state in which the coating film is completely peeled off while measuring frictional wear characteristics in a lubricating environment using automobile engine oil.

In addition, Table 1 below summarizes the physical properties of commercial coatings applied to the main engine parts.

Coating material friction Hardness Toughness (residual stress) Heat resistance Cr-N + + +++ +++ W-C: H ++ ++ ++ ++ DLC +++ +++ + +

(+ Lack, ++ moderate, +++ excellent)

As shown in Table 1 above, the biggest drawback of DLC having excellent physical properties compared to other coating techniques is shown to be low temperature properties. Therefore, it is necessary to develop a coating layer to improve the weakness of the DLC properties, and when the high temperature properties of the DLC are improved, it is expected to be applied to various fields, and is an automotive parts field such as an automobile cylinder liner and a piston ring. In addition, it is expected to be applicable to various semiconductor equipment jigs.

The present invention has been made to solve the conventional problems as described above, by controlling the physical properties of the film using a fluoride on the surface of the DLC coating layer formed on the surface of the substrate, corrosion resistance and abrasion resistance, etc. according to the environment of use of the product The present invention provides a method for producing a thin film containing fluorine and a thin film for improving the physical properties of the film.

The thin film manufacturing method of the present invention for achieving the above object is, after coating the DLC layer on the surface of the substrate, characterized in that for coating the fluorine layer using a fluoride gas on the surface of the DLC layer. .

CF ₄ may be used as the fluoride.

The thin film manufacturing method of the present invention includes a pretreatment step of pretreating the surface of the substrate by inputting a reaction gas for activating the surface of the substrate and removing residual organic matters in the chamber; An intermediate layer forming step of coating an intermediate layer on the surface of the substrate by injecting a reaction gas containing Si to improve adhesion within the chamber; A DLC layer forming step of coating a DLC layer on the surface of the intermediate layer by injecting hydrocarbon gas into the chamber; And a fluorine layer forming step of coating a fluorine layer on the surface of the DLC layer by injecting a fluoride gas to improve corrosion resistance and abrasion resistance inside the chamber.

In the pretreatment step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and H ₂ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, and a pulsed voltage is applied to the substrate to plasma the surroundings. The surface of the substrate may be ion activated for 10 to 30 minutes in the state where it is generated and maintained.

In the intermediate layer forming step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and tetramethylsilane (TMS) are introduced into the chamber at a volume ratio of 1: 0.1-5, but a pulsed voltage is applied to the substrate. Thus, an intermediate layer containing silicon (Si) may be deposited on the surface of the activated substrate for 10-30 minutes while the plasma is generated and maintained around it.

In the DLC layer forming step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and C ₂ H ₂ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, by applying a pulsed voltage to the substrate. While the plasma is generated and maintained around the DLC layer containing carbon (C) for 30 to 120 minutes on the surface of the intermediate layer may be deposited.

In the fluorine layer forming step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and CF ₄ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, but a pulsed voltage is applied to the substrate to The fluorine layer containing fluorine (F) may be deposited on the surface of the DLC layer for 10 to 30 minutes while the plasma is generated and maintained.

In the DLC layer forming step, the hydrocarbon gas may be a hydrocarbon gas having a minimum content of hydrogen.

In the fluorine layer forming step, the coefficient of friction and the corrosion resistance of the thin film can be controlled according to the amount of fluorine is added.

The thin film structure of the present invention comprises: an intermediate layer coated with silicon (Si) to improve adhesion on the surface of the substrate; DLC layer containing the carbon (C) is coated on the surface of the intermediate layer; And a fluorine layer coated with fluorine (F) on the surface of the DLC layer.

The present invention through the above problem solving means, there is an effect that can improve the physical properties of the surface of the thin film according to the environment for the product to be used by controlling the amount of fluorine after depositing the DLC film.

In particular, in the case of parts requiring hardness and durability, such as automobile parts, the adhesion is enhanced through the interlayer coating containing Si, and the friction coefficient is improved by the surface layer by adding a relatively small amount of fluorine, thereby improving hardness and durability. It can be applied to parts that require.

In addition, in the case of products requiring corrosion resistance due to the extreme environment, by adding a relatively high content of fluorine to make the surface hydrophobic, so that the wettability to the surface is reduced to products that require high corrosion resistance such as semiconductor jig There is also an effect that can be applied.

1 is a view showing a state in which the coating film is completely peeled off during the measurement of friction wear characteristics in a lubricating environment using automotive engine oil,
2 is a view showing the overall structure of a thin film coated on the substrate by the method for manufacturing a thin film of the present invention,
3 is a view showing a coating picture of a sample produced by the thin film manufacturing method according to the present invention,
4 is a view showing a Raman measurement result according to the CF ₄ gas addition amount according to the present invention,
5 is a view showing the analysis of the SEM surface and cross-sectional photograph of the specimen coated by the present invention,
6 and 7 is a view showing the change in hardness value and elastic modulus of the thin film according to the addition of CF ₄ gas according to the present invention and the corresponding H / E index,
8 is a view showing the adhesion test results of the DLC thin film according to the CF₄ gas addition according to the present invention,
9 is a view showing the evaluation of wear characteristics measured in a dry environment and a wet environment according to the amount of CF₄ gas according to the present invention,
10 is a view showing a contact angle measurement results according to the CF₄ gas addition amount according to the present invention,
11 is a view showing the content of fluorine in the DLC coating layer in the present invention, and the results of the coin position according to the addition of Si, F,
12 is a view showing the salt spray measurement results for DLC thin film in the present invention,
13 is a view showing an example in which the thin film according to the present invention is applied to a metal mask,
14 is a view showing a comparison of the characteristics before and after the application of the product at the time of solder screen printing with a thin film according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

2 is a view showing the overall structure of a thin film coated on the substrate according to the present invention.

Referring to the drawings, the method for producing a thin film containing fluorine according to the present invention is to pretreat the surface of the substrate 10 by injecting a reaction gas for activating the surface of the substrate 10 and removing residual organic matters inside the chamber. A pretreatment step and an intermediate layer forming step of coating the intermediate layer 20 on the surface of the substrate 10 by adding a reaction gas containing Si to improve the adhesion inside the chamber, and a hydrocarbon gas is introduced into the chamber. DLC layer forming step of coating the DLC layer 30 on the surface of the intermediate layer 20 and a fluoride gas is added to the inside of the chamber to improve corrosion resistance and abrasion resistance to fluorine on the surface of the DLC layer 30. It consists of a fluorine layer forming step of coating the lean layer (40).

That is, after coating the DLC layer 30 on the surface of the substrate 10, by coating the fluorine layer 40 using a fluoride gas on the surface of the DLC layer 30, fluorine (F) As a result of the formation of a porous tissue, due to the hydrophobic (hydrophobic) surface is due to the low wettability to the surface is increased corrosion resistance.

In particular, it is possible to apply the automotive parts that require durability by improving the coefficient of friction by the surface layer that acts as a forge of the oil while having durability against MoDTC (GF4) oil, which is a next-generation automotive lubricating oil.

In the present invention, the pre-treatment step, while maintaining the pressure in the chamber to 10mTorr ~ 500mTorr, while putting Ar and H ₂ in a volume ratio of 1: 0.1 to 5 inside the chamber, the pulse type voltage to the substrate 10 The surface of the substrate 10 may be ion-activated for 10 to 30 minutes in a state where plasma is generated and maintained therebetween.

Specifically, after the base 10 is charged into the chamber, the vacuum inside the chamber is evacuated to a vacuum of 3 x 10 ^-3 Torr using a vacuum pump 41 such as a rotary pump and a booster pump.

Thereafter, while maintaining the pressure inside the chamber at a process pressure between 10 mTorr and 500 mTorr, a reaction gas of Ar and H ₂ is introduced into the chamber at a volume ratio of 1: 0.1 to 5 through a gas inlet device. . At this time, the substrate 10 is subjected to a pulsed bias voltage through a power supply to generate and maintain a plasma, thereby causing a chemical reaction in the plasma to activate (etch) the surface of the substrate 10 and simultaneously process it by organic cleaning. The remaining organic matter on the surface of the substrate 10 that is not obtained is removed (cleaned).

In the intermediate layer forming step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and tetramethylsilane (TMS) are introduced into the chamber at a volume ratio of 1: 0.1 to 5, but the pulse type is applied to the substrate 10. By applying a voltage, the intermediate layer 20 containing silicon (Si) may be deposited on the surface of the activated substrate 10 for 10-30 minutes while the plasma is generated and maintained around the voltage.

Specifically, in a state in which the pressure inside the chamber is maintained at a process pressure between 10 mTorr and 500 mTorr, a reaction gas of Ar and tetramethylsilane (TMS: Si (CH ₃ ) ₄ ) 1 is introduced into the chamber through a gas inlet unit. : Insert in volume ratio of 0.1 ~ 5. In this case, the intermediate layer 20 is coated on the substrate 10 in a state in which a plasma is generated by applying a pulsed bias voltage through a power supply.

Here, the gas used in the intermediate layer 20 is not limited to tetramethylsilane, and other compound gas containing Si may be applied.

In the DLC layer forming step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and C ₂ H ₂ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, but the pulse type voltage is applied to the substrate 10. It is possible to deposit and form a DLC layer 30 containing carbon (C) for 30 to 120 minutes on the surface of the intermediate layer 20 in a state where the plasma is generated and maintained around it.

Specifically, while maintaining the pressure inside the chamber at a process pressure between 10 mTorr and 500 mTorr, a reaction gas of Ar and C ₂ H ₂ is introduced into the chamber at a volume ratio of 1: 0.1-5 through a gas inlet unit. do. In this case, the substrate 10 is coated with the DLC layer 30 while generating and maintaining a plasma by applying a pulsed bias voltage through a power supply.

Here, the gas used in the intermediate layer 20 is not limited to C ₂ H ₂ , but other hydrocarbon gases may be applied. However, in the present invention, it is advantageous to minimize the content of hydrogen, and preferably C ₂ H ₂ should be used.

In the fluorine layer forming step, the pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and CF ₄ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, but a pulsed voltage is applied to the substrate 10. Thus, the fluorine layer 40 containing fluorine (F) may be deposited on the surface of the DLC layer 30 for 10 to 30 minutes while the plasma is generated and maintained around it.

Specifically, while maintaining the pressure inside the chamber at a process pressure between 10 mTorr and 500 mTorr, a reaction gas of Ar and CF ₄ is introduced into the chamber at a volume ratio of 1: 0.1 to 5 through a gas inlet device. In this case, the substrate 10 is coated with the fluorine layer 40 while generating and maintaining a plasma by applying a pulsed bias voltage through a power supply.

Here, the gas used in the intermediate layer 20 is not limited to CF ₄ , and other gases of fluoride may be applied.

In the fluorine layer forming step, the coefficient of friction and the corrosion resistance of the thin film may be controlled according to the amount of fluorine (F) added.

In other words, in the case of automotive parts, an optimum Si-Interlayer layer was deposited to increase adhesion. At this time, the coefficient of friction is improved by the surface layer acting as a forge of oil by adding 3 to 5% of fluorine (F), thereby improving hardness and durability. Make it possible to apply the necessary automotive parts.

At this time, when the total thickness of the thin film is 2.3㎛, among them, the Si-Interlayer is designed to a thickness of about 0.5㎛ to increase the adhesion, and the thickness of the DLC coating layer was based on a thickness of 1㎛, in the case of the fluorine layer 40 Designed to a thickness of about 0.8㎛ to maintain the hardness and improve the coefficient of friction through fluorine (F).

On the other hand, in the case of a semiconductor jig that requires corrosion resistance due to the extreme environment, the surface becomes hydrophobic by adding 10 to 20% of fluorine (F), and thus the surface is not wetted (contact angle about 126 °). Will increase.

At this time, the total thickness of the thin film showed a phenomenon that the surface is etched as the content of fluorine (F) increased, which represented a thickness of 1.8 μm, which is smaller than 2.3 μm, which causes a decrease in hardness and adhesion. However, in the case of semiconductor jig, corrosion resistance should be better than hardness and adhesion, so that the contact angle is increased to 126 ° by increasing the amount of fluorine (F), thereby making the film hydrophobic and increasing the corrosion resistance. .

Therefore, if the membrane is designed in consideration of the environment of use of the product by adjusting the amount of fluorine (F), it is possible to make an optimal multilayer film and to apply it to various fields.

On the other hand, the thin film containing the fluorine (F) of the present invention, on the surface of the substrate 10, the silicon (Si) is contained and coated to improve the adhesion to the surface of the intermediate layer 20, It may be configured to include a DLC layer 30 coated with carbon (C), and a fluorine layer 40 coated with fluorine (F) on the surface of the DLC layer 30.

In addition, in the fields to which the above thin film coating technology is applied, not only low friction coating, but also various technologies such as nitriding, oxynitride, and PVD for durability of automobile parts are required.

Therefore, it is advantageous to include equipment capable of nitriding and oxynitridation in PECVD equipment for forming DLC film, and may be improved to apply to the immersion nitriding and high toughness coating technology required in the field of construction machinery. .

As such, the typical characteristics of PECVD equipment are gaseous raw materials, which makes it easier to secure uniformity compared to PVD processes using solid targets, and it is possible to simultaneously and uniformly process complex and various products. In addition, if it is possible to secure gaseous raw materials, the application of various materials may be possible simultaneously in one chamber.

In the thin film manufacturing apparatus according to the present invention, a large-scale PECVD equipment is used to derive the optimal physical property DLC coating layer using a large-area process plasma, and the size of the equipment is 1.5m X 1.5m with an effective space of 1.5m x 1.5m. It would be desirable to have a size that can be processed uniformly. In addition, as described above, the thin film manufacturing apparatus is appropriately applied to the coating equipment of the dual (DUPLEX) capable of nitriding and DLC coating.

The operation and effects of the present invention will be described with reference to the accompanying drawings.

Looking at the embodiment for the thin film manufacturing method of the present invention, Ar 1 ~ 500sccm and H ₂ 1 ~ 500sccm in the state of maintaining the pressure to 10mTorr ~ 500mTorr inside the chamber, and the appropriate temperature for pretreatment by the heater is added. . Then, a pulsed voltage is applied to the substrate 10 to ion-activate the surface of the substrate 10 for 20 minutes while the plasma is generated and maintained around the substrate 10.

Thereafter, Ar 1 to 500 sccm and tetramethylsilane (TMS) 1 to 100 sccm were introduced into the chamber, and plasma was generated around the substrate 10 for 15 minutes on the surface of the ion-activated substrate 10. The intermediate layer 20 is coated.

Subsequently, Ar 1 to 500 sccm and C ₂ H ₂ 1 to 500 sccm are introduced into the chamber, and the DLC layer 30 is applied to the surface of the intermediate layer 20 for 1 hour while a plasma is generated around the substrate 10. Vapor deposition.

Then, Ar 1 to 500 sccm and CF ₄ 1 to 100 sccm are introduced into the chamber, and the fluorine layer 40 is deposited on the surface of the DLC layer 30 for 10 minutes while a plasma is generated around the substrate 10. Form.

3 shows a coating picture of the sample prepared by the above-described thin film manufacturing method, Table 2 below summarizes the physical properties of the thin film prepared by the present invention.

Hardness (GPa) Coefficient of friction Adhesion (N) Contact angle (°) Thickness (㎛) 18-21 0.04-0.2 18 ~ 32 69-126 1-3

4 is a graph showing a Raman measurement result according to the amount of CF ₄ gas added in the fluorine layer forming step. Referring to the drawings, as the amount of CF4 gas increases, the intensity (intensity) of the G peak appears to increase and the peak position also increases.

In addition, the change in the content of each element present in the DLC calculated based on the results of the Elastic Recoil Detection (ERD) is summarized in Table 3 below.

CF ₄ gas volume Element content (%) C H F 0 sccm 93.90 6.10 0 10 sccm 80.98 16.60 2.43 20 sccm 81.30 13.01 5.69 30 sccm 83.68 9.63 6.69 40 sccm 80.66 9.67 9.67 50 sccm 77.52 6.98 15.50

The content of fluorine (F) is shown to increase in proportion to the CF ₄ gas content used.

5 is a result of analyzing the SEM surface and cross-sectional photograph of the specimen coated by the present invention.

Referring to the drawings, it is observed that the thickness of the formed layer is different depending on the gas composition used. In addition, the thickness of the coating layer was the lowest thickness observed in the thin film containing no fluorine (F), the higher thickness is shown in the thin film containing CF ₄ .

The reason for this is that the deposition rate is increased by further depositing the fluorine layer 40 after the DLC layer 30 is coated. As a result, when the flow rate of CF4 gas increases, the thickness of the thin film decreases gradually as the CF4 gas flow rate increases. It can be seen that this is because the thickness of the thin film is reduced due to the addition of fluorine (F) to the porous structure (porous) and the structure of the ingested properties, thereby showing a tendency to decrease the hardness.

6 and 7 show the change in hardness value and modulus of elasticity of the DLC thin film according to the addition of CF₄ gas and the H / E index accordingly.

Referring to FIGS. 6 and 7, the highest hardness value of 21.4 GPa was shown in the thin film containing 10% of fluorine (F), and the content of fluorine (F) was increased to 18.2 GPa. The trend is decreasing.

As described above, the hardness is reduced as the surface tissue is porous and changes to the tissue of the ingested properties. In addition, the thin film without fluorine (F) was measured at about 20 GPa, which corresponds to the maximum hardness value that can be produced by PECVD.

In general, it is known that the durability or wear resistance of the coating layer can be predicted by the H / E value. However, when the flow rate of CF ₄ increases as shown in FIG. 7, the E value is low at the same hardness value.

Figure 8 shows the adhesion test results of the DLC thin film according to the CF₄ gas addition.

Referring to the drawings, when fluorine (F) was not added in the evaluation of the effect on the adhesion, showed a high adhesion of 32.7 N, but the adhesion of 18.4 ~ 29.5 N by the addition of fluorine (F) Appeared. However, the adhesive force of the thin film manufactured by the present invention is a high value that can be applied to automobile driving parts, and the specimen under the process conditions showing the adhesion force of about 18 N also has sufficient adhesion force that can be used as the functional specimen.

9 is a view showing the evaluation of wear characteristics measured in a dry environment and a wet environment by the ball on disc method according to the amount of CF₄ gas.

Referring to the drawings, in the dry environment, the coefficient of friction tends to increase with increasing fluorine (F) content, while GF3 oil, which is an automobile lubricant, shows almost the same coefficient of friction. However, DLC coatings prepared by the general PECVD method for measuring the friction coefficient in GF4 oil are known to be completely peeled off during the abrasion test, as shown in the left figure in the wear track picture, but rather by the addition of fluorine (F). The coefficient is good and the width of the friction track after the friction test is very good.

As a result, it has been confirmed that the porous structure formed by the addition of fluorine (F) gas is excellent in the coefficient of friction by the surface layer serving as the oil forge while being durable against GF4 oil.

FIG. 10 is a view illustrating a friction coefficient evaluation result measured in a low friction oil (MO-DTC) (GF4) environment according to various deposition methods.

Referring to the drawings, DLC coated with the fluorine of the present invention shows a low coefficient of friction characteristics compared to DLC coated by PVD or PECVD, and has a better coefficient of friction than DLC coated by a general DLC manufacturing method. It can be secured.

11 shows the contact angle measurement results according to the amount of CF₄ gas added.

Referring to the drawings, as the content of fluorine (F) increases the contact angle in the absence of fluorine (F), it appears to increase almost proportionally from 69 ° to 126 °. It can be seen that this hydrophobic property is shown as an excellent coefficient of friction in the lubrication environment.

FIG. 12 is a graph showing the results of a coincidence measurement according to the amount of CF ₄ gas and Si, CF ₄ added to the DLC coating layer.

Referring to the drawings, it was found that the corrosion resistance increases as the content of fluorine (F) increases, which is confirmed because the reaction with brine is minimized because of less wettability. On the other hand, when comparing the DLC with no element, the Si-added specimen, and the fluorine (F) -added specimen, the Si-added specimen was found to be somewhat poor in corrosion resistance. ) Is more than five times better corrosion resistance than the other two cases.

In particular, the DLC layer coated under optimum conditions was found to be stable without corrosion, as shown in FIG. 13, for at least 2000 hours. Thus, in the case of the specimen to which fluorine (F) was added, excellent corrosion resistance can be expected.

On the other hand, as an application field of the thin film manufactured by the present invention, the main parts of the automotive field are representative.

FIG. 14 illustrates a representative part (left) to which a coating technology is applied in a vehicle and a driving part (right) to which a DLC coating is applied, and FIG. After, the picture is shown.

As shown in the accompanying drawings, the thin film according to the present invention can be applied to more various automotive parts, such as tappets, valves, piston rings, cylinder liners, etc. in the situation where the use of low friction oil in the future automotive field is required, the use thereof The scope of the present invention is very broad, and in particular, as the need for preparing a countermeasure to cope with high environmental costs such as the recent CO ₂ emission regulation, and the coating technology as a way to improve the fuel economy of the car can be applied to the thin film of the present invention There is this.

In addition, as another application field of the thin film manufactured according to the present invention, in addition to the above-described automotive field, it can be applied to a metal mask, a semiconductor mold, and various components requiring corrosion resistance.

Referring to FIG. 16, the coefficient of friction was improved by at least 10 times through the application of the thin film of the present invention to a metal mask product which was previously used without coating, thereby improving the wettability of the solder and thus the lifetime of the related product (based on the usage time). It is improved by 5 times.

In addition, as shown in Figure 17, because of the excellent physical properties of the thin film of the present invention to improve the uniform solder distribution and accuracy.

In addition, DLC coating was performed on an invar material having a thickness of 30 μm, which is a semiconductor jig used to make a semiconductor chip for LEDs, and a uniformity of thickness about 100 × 30 cm was confirmed. In addition, by effectively generating a DLC coating layer without damage to the thin specimen, it is possible to minimize the cost and processing cost of the existing jig material.

On the other hand, the present invention has been described in detail only with respect to the specific examples described above it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, it is natural that such variations and modifications belong to the appended claims. .

10: base material 20: intermediate layer
30: DLC layer 40: fluorine layer

Claims (10)

After the DLC layer 30 is coated on the surface of the substrate 10, the fluorine layer 40 is coated on the surface of the DLC layer 30 using a gas of fluoride;
The fluoride is a thin film manufacturing method containing fluorine, characterized in that CF ₄ is used. delete A pretreatment step of pretreating the surface of the substrate 10 by injecting a reaction gas for activating the surface of the substrate 10 and removing residual organic materials in the chamber;
An intermediate layer forming step of coating the intermediate layer 20 on the surface of the substrate 10 by injecting a reaction gas containing Si to improve adhesion within the chamber;
DLC layer forming step of coating the DLC layer 30 on the surface of the intermediate layer 20 by injecting hydrocarbon gas into the chamber; And
And a fluorine layer forming step of coating a fluorine layer 40 on the surface of the DLC layer 30 by injecting a fluoride gas to improve corrosion resistance and abrasion resistance inside the chamber.
The fluorine layer forming step,
The pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and CF ₄ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, and a plasma is generated around the substrate 10 by applying a pulsed voltage. The fluorine-containing thin film manufacturing method characterized in that the deposition of a fluorine layer (40) containing fluorine (F) for 10 to 30 minutes on the surface of the DLC layer 30 in the maintained state. The method of claim 3, wherein
The pre-
The pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and H ₂ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, and a plasma voltage is generated around the substrate 10 by applying a pulsed voltage. Method for producing a thin film containing fluorine, characterized in that the surface of the substrate 10 is ion-activated for 10 to 30 minutes in a maintained state. The method of claim 3, wherein
The intermediate layer forming step,
The pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and tetramethylsilane (TMS) are introduced into the chamber at a volume ratio of 1: 0.1 to 5, and a pulsed voltage is applied to the substrate 10 to thereby surround the chamber. Fluorine-containing thin film manufacturing method characterized in that the deposition of the intermediate layer (20) containing silicon (Si) for 10-30 minutes on the surface of the activated substrate (10) while the plasma is generated and maintained. The method of claim 3, wherein
The DLC layer forming step,
The pressure inside the chamber is maintained at 10 mTorr to 500 mTorr, and Ar and C ₂ H ₂ are introduced into the chamber at a volume ratio of 1: 0.1 to 5, and a pulsed voltage is applied to the substrate 10 to plasma the surroundings. The fluorine-containing thin film manufacturing method, characterized in that by depositing to form a DLC layer (30) containing carbon (C) for 30 to 120 minutes on the surface of the intermediate layer 20 in the state maintained. delete The method of claim 3, wherein
In the DLC layer forming step, the hydrocarbon gas is a fluorine-containing thin film manufacturing method, characterized in that the hydrocarbon gas is used to minimize the content of hydrogen. The method of claim 3, wherein
In the fluorine layer forming step, the fluorine-containing thin film manufacturing method, characterized in that the friction coefficient and the corrosion resistance of the thin film is controlled according to the amount of fluorine (F) is added. An intermediate layer 20 coated with silicon (Si) to improve adhesion to the surface of the substrate 10;
DLC layer 30 is coated by containing the carbon (C) on the surface of the intermediate layer 20; And
And a fluorine layer 40 coated with fluorine (F) by the gas of fluoride on the surface of the DLC layer 30.
The fluoride is a thin film containing fluorine characterized in that the coating using CF ₄ .

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