Multilayer coating for interface cones

Abstract

A multi-layer coating is disclosed that includes an adhesion layer and a protective coating. The multi-layer coating can be applied to a portion of at least one of the substrate and tip of the interface cone. Also disclosed is a method of making the coated interface cone.

Description

Technical Field

[0001] [Related Applications] This application claims priority to U.S. Provisional Patent Application No. 63 / 179,956, filed Apr. 26, 2021, which is hereby incorporated by reference in its entirety.

[0002] The present disclosure generally relates to multi-layer coatings including an adhesive layer and a protective coating. The multi-layer coating can be applied to at least a portion of a substrate of an interface cone and a chip. A method of manufacturing a coated interface cone is also disclosed.

Background Art

[0003] The interface cone of an inductively coupled plasma mass spectrometer (ICP-MS) consists of a sampler cone and a skimmer cone, which transport ions from the plasma to the mass spectrometer. The tip region of the interface cone is exposed to high temperatures (about 1000° C. near the orifice) and highly corrosive acids. The interface cone can include a tip and a base.

[0004] For both the sampler cone and the skimmer cone, the tip can be made of nickel or platinum. Nickel tips are a standard and economical option suitable for most applications. Platinum tips, although more expensive, are required for highly concentrated acids and are used in the semiconductor industry. Platinum tips can be of different sizes, and the larger the size, the higher the cost.

[0005] For the sampler cone, the material of the base is copper due to its excellent thermal conductivity, but copper has no resistance to acids. In a sampler cone with a platinum tip, the material of the copper base corrodes and detaches from the platinum tip, thereby causing an early failure of the interface cone.

[0006] Regarding skimmer cones, the base material is nickel, regardless of whether the tip is nickel or platinum. However, nickel is not resistant to aggressive acids, such as sulfuric acid, phosphoric acid, hydrofluoric acid, or organic matrices.

[0007] For many applications, such as in the semiconductor industry, transition metals, like copper and nickel, are the target analytes, and it is crucial to reduce background signals and lower the detection limit. Therefore, the presence of copper and nickel in the interface cone (substrate and / or chip) is considered to cause an increase in background signals, and their use is not permitted in the semiconductor industry.

[0008] Traditionally, platinum coatings have been applied to interface cones. However, coating a cone with platinum to a thickness of approximately 20 μm, for example, by ion plating or plasma chemical deposition, is extremely expensive. Furthermore, copper from the cone's substrate diffuses into the platinum coating, increasing the background signal. In other cases, the cone is coated with gold. However, gold has a low melting point, especially lower than nickel, and readily dissolves in the corrosive acids commonly used in ICP-MS, making gold coatings unsuitable.

[0009] During the lifespan of the interface cone, salts and / or oxides accumulate on the surface, requiring cleaning to maximize performance and equipment productivity. Having an interface cone that requires minimal cleaning is considered advantageous.

[0010] Thus, a multilayer coating that can be applied to a portion of the interface cone is needed. A multilayer coating can provide one or more benefits, including reducing background signals caused by the presence of Cu and Ni in the interface cone, resistance to high temperatures and corrosive acids, and minimizing the frequency of cleaning the interface cone.

[0011] The features of this disclosure are illustrated as examples and are not limited to the following figures; similar numbers represent similar elements. [Brief explanation of the drawing]

[0012] [Figure 1] This is a multilayer coating according to one aspect of the present invention. [Figure 2] This is a multilayer coating according to another aspect of the present invention. [Figure 3] This is a multilayer coating according to another aspect of the present invention. [Figure 4] This is a multilayer coating according to another aspect of the present invention. [Figure 5] This is a diagram of a comparative interface cone that includes a protective coating but lacks an adhesive layer. [Figure 6] This is an energy-dispersive spectroscopy (EDS) mapping of an interface cone having a multilayer coating according to one aspect of the present invention. [Figure 7A] This is a diagram of an interface cone having a multilayer coating according to one aspect of the present invention. [Figure 7B] This is a scanning electron microscope (SEM) image showing various nanostructures formed on the substrate of the interface cone. [Figure 7C] This is an EDS mapping for an interface cone having a multilayer coating according to one aspect of the present invention. [Figure 8A] This is a diagram of an interface cone having a multilayer coating according to one aspect of the present invention. [Figure 8B]It is a scanning electron microscope (SEM) image showing various nanostructures formed on the substrate of the interface cone. [Figure 8C] It is an EDS mapping of an interface cone having a multilayer coating according to one aspect of the present invention. [Figure 9A] The interface cone is shown. [Figure 9B] The interface cone is shown. [Figure 9C] The interface cone is shown. **Summary of the Invention**

[0013] In one aspect, a multilayer coating including an adhesive layer and a protective coating is disclosed.

[0014] In another aspect, a method for manufacturing a coated interface cone is disclosed, which includes preparing an interface cone having a substrate and a chip, depositing an adhesive layer on at least a portion of the substrate and the chip, and depositing a protective layer.

[0015] Further features and advantages in various embodiments are partially described in the following description, and may be partially apparent from the description, or obtained by implementing various embodiments. The objects and other advantages of various embodiments are realized and achieved by using the elements and combinations specifically pointed out herein. **Modes for Carrying Out the Invention**

[0016] This disclosure is explained by referring to its examples for the purpose of simplicity and illustration. In the following description, numerous specific details are shown to provide a thorough understanding of this disclosure. However, it will be readily apparent that this disclosure can be implemented without being limited to those specific details. Some methods and structures are omitted to avoid obscuring this disclosure.

[0017] Also, the elements in the accompanying figures may include additional components, and some of the components in the figures can be excluded and / or modified without departing from the scope of the present disclosure. The elements in the figures may not be in exact proportions, and thus, the elements may have different sizes and / or configurations than those in the figures. Any reference to "upper" or "bottom" is for ease of understanding the relative position with respect to another element and should not be considered limiting. When there are more than one element present, for ease of understanding, they are referred to as the first element, the second element, the third element, and so on.

[0018] This specification describes coatings and articles in their broad and diverse embodiments, such as ion transfer devices comprising coatings, and methods of manufacturing and using coatings and articles.

[0019] Figure 1 describes a multilayer coating 10 comprising an adhesive layer 12 and a protective coating 14 in the present disclosure. The multilayer coating 10 can be deposited on a portion of the interface cone 18 and serves to transport ions from the plasma to the mass spectrometer. The protective coating 14 can extend the life of the interface cone 18. The protective coating 14 can also reduce the material from the substrate 20 of the interface cone 18 by generating a background signal. The adhesive layer 12 can improve the adhesion of the protective coating 14 to a portion of the surface of at least one of the substrate 20 and the chip 22. In one aspect, the diffusion barrier 16 is included in the multilayer coating 10 and can reduce and / or limit the diffusion of ions from the material of the substrate 20 to the protective coating 14.

[0020] The protective coating 14 may be exposed to corrosive acids at a temperature of approximately 1000°C. For this reason, the protective coating 14 may have a melting temperature higher than approximately 1000°C. In one embodiment, the protective coating 14 may have a melting temperature higher than the melting temperature of the material present in the tip of the interface cone. For example, if the tip of the interface cone is nickel, the protective coating 14 may have a melting temperature higher than the melting temperature of nickel, e.g., approximately 1455°C. Similarly, if the tip of the interface cone is platinum, the protective coating 14 may have a melting temperature higher than the melting temperature of platinum, e.g., approximately 1768°C.

[0021] The protective coating 14 may be insoluble in acids having a pH in the range of approximately 1 to approximately 7. The protective coating 14 may be resistant to the corrosive effects of acids used in mass spectrometers, such as inductively coupled plasma mass spectrometers. The protective coating may be insoluble in bases and organic solutions, and may be insoluble in acids having a pH < 1. The protective coating may be resistant to damage from ionic shocks caused by plasma. The protective coating may be resistant to interactions with organic solutions and carbide formation.

[0022] The protective coating 14 can be present in the multilayer coating 10 with a thickness ranging from approximately 0.05 μm to approximately 19 μm, for example, approximately 0.1 μm to approximately 15 μm, and in further examples, approximately 0.75 μm to approximately 12 μm. In one embodiment, the protective coating 14 can be present with a thickness of less than approximately 6 μm, for example, approximately 2 μm to approximately 6 μm. In one embodiment, the protective coating 14 can be present in the multilayer coating 10 with a thickness that provides the interface cone 18 with resistance to corrosive acids and / or high temperatures.

[0023] The protective coating 14 may be a single layer of platinum with a thickness of approximately 2 μm to approximately 6 μm, for example, approximately 4 μm or more. The protective coating 14 may have a purity higher than approximately 95% and a density close to that of the bulk material of the protective coating. For example, if the protective coating is composed of platinum, the protective coating may have a density of approximately 21.45 g / cm³. 3 It may have a density close to that of bulk platinum. The protective coating 14 can be applied by using a sputtering deposition process (e.g., up to a thickness of approximately 4 μm) or an electroplating deposition process (e.g., up to a thickness of approximately 6 μm).

[0024] The multilayer coating 10 may include an adhesive layer 12. The adhesive layer 12 can be made of any material that can enhance adhesion between the protective coating 14 and the substrate 20 and / or the chip 22 material. The adhesive layer 12 can be made of at least one material selected from titanium, chromium, tungsten, and combinations thereof. The adhesive layer 12 may be a single layer. The adhesive layer 12 may also consist of one or more layers, for example, a first adhesive layer 12a, a second adhesive layer 12b, and so on. If the adhesive layer 12 consists of more than one layer, the adhesive layer 12 may be made from the same or different materials, including combinations of different materials.

[0025] The adhesive layer 1 can exist in the multilayer coating with a thickness ranging from approximately 10 nm to approximately 500 nm, for example, approximately 15 nm to approximately 475 nm, and in further examples, approximately 20 nm to approximately 450 nm.

[0026] The multilayer coating 10 can be applied to at least one portion of the interface cone's substrate 20 and tip 22. For example, if the substrate 20 is nickel, the adhesive layer 12 may be sputtered titanium or chromium, and the protective layer 14 may be sputtered platinum, as shown in Figure 1.

[0027] In another embodiment, as shown in Figure 3, the adhesive layer 12 may consist of multiple layers, for example, a first adhesive layer 12a and a second adhesive layer 12b. The second adhesive layer 12b may be sputtered titanium or chromium. The first adhesive layer 12a may be sputtered platinum, which can function as an adhesive layer for the protective layer 14. The protective layer 14 may be electroplated platinum.

[0028] The multilayer coating 10 may include a diffusion barrier layer 16. The diffusion barrier layer 16 can be applied to the surface of the interface cone 18. The diffusion barrier layer 16 can be made of one or more materials that can reduce and / or prevent the diffusion of ions from the material of the substrate 20 into the protective coating 14. In one embodiment, the diffusion barrier layer 16 can be made of at least one material selected from electrolytic nickel, electroless nickel and combinations thereof.

[0029] The diffusion barrier layer 16 can exist with a thickness exceeding approximately 500 nm, for example, approximately 2 μm to approximately 30 μm, and in further examples, approximately 4 μm to approximately 25 μm.

[0030] As shown in Figure 2, when the substrate 20 is copper, the multilayer coating 10 may further comprise a nickel diffusion barrier 16. The multilayer coating 10 may also comprise a sputtered titanium or chromium adhesive layer 12 and a sputtered platinum protective layer 14.

[0031] In another embodiment, as shown in Figure 4, the adhesive layer 12 may consist of multiple layers, for example, a first adhesive layer 12a and a second adhesive layer 12b. The second adhesive layer 12b may be sputtered titanium or chromium. The first adhesive layer 12a may be sputtered platinum, thereby functioning as an adhesive layer to the protective layer 14. In this case, the first adhesive layer 12a is not intended to increase the thickness of the protective layer 14. The protective layer 14 may be electroplated platinum.

[0032] The interface cone 18 may include a substrate 20 and a chip 22, wherein a portion of at least one of the substrate 20 and the chip 22 is coated with the disclosed multilayer coating 10. In one embodiment, the entire surface of the chip 22 is coated with the disclosed multilayer coating 10. In another embodiment, less than 100% of the surface of the chip 22 is coated with the disclosed multilayer coating 10. In one embodiment, the entire surface of the substrate 20 is coated with the disclosed multilayer coating 10. In another embodiment, less than 100% of the surface of the substrate 20 is coated with the disclosed multilayer coating 10. In yet another embodiment, the entire surfaces of both the substrate 20 and the chip 22 are coated with the disclosed multilayer coating 10. In yet another embodiment, less than 100% of each surface of the substrate 20 and the chip 22 is coated with the disclosed multilayer coating 10.

[0033] The substrate 20 can be made from at least one material selected from copper and nickel. The tip 22 can be made from at least one material selected from nickel and platinum. In one embodiment, the interface cone 18 may comprise a substrate 20 made of copper and a tip 22 made of platinum. The multilayer coating 10 may also comprise a nickel diffusion barrier layer.

[0034] A method for manufacturing a coated interface cone may include preparing an interface cone 18 having a base material 20 and a tip 22. An adhesive layer 12 can be deposited on at least one portion of the base material 20 and the tip 22. A protective layer 14 can be deposited on the adhesive layer 12.

[0035] The protective layer 14 can be deposited using conventional deposition techniques. In one embodiment, the protective layer 14 can be deposited by sputtering platinum. In another embodiment, the protective layer 14 can be deposited by electroplating platinum. Other deposition techniques, but not limited to these, include thermal deposition, electron beam deposition, chemical deposition, and atomic layer deposition.

[0036] In one embodiment, the adhesive layer 12 can be deposited using standard deposition techniques. In another embodiment, the adhesive layer 12 can be deposited by sputtering.

[0037] The interface cone 18 may comprise a copper substrate 20. In one embodiment, the multilayer coating 10 may further include depositing an adhesive layer 12 after depositing a diffusion barrier layer 16. The diffusion barrier layer 16 can be made from at least one material selected from electrolytic nickel, electroless nickel, and combinations thereof. [Examples]

[0038] [Comparative Example 1] As shown in Figure 5, an interface cone 18 having the material of a copper substrate 20 and the material of a nickel chip 22 was coated with a single layer of platinum by electron beam deposition. The platinum coating did not adhere to the material of the copper substrate 20 or the nickel chip 22. When Scotch® tape was applied to the chip 22 and the substrate 20 and then peeled off, the platinum coating also peeled off from both the copper substrate 20 and the nickel chip 22.

[0039] [Example 1] An interface cone 18 having a copper substrate 20 and a nickel tip 22 was coated with a multilayer coating 10 including a protective coating 14 and an adhesive layer 12. As the adhesive layer 12, titanium was deposited on at least one portion of the copper substrate 20 and the nickel tip 22 by sputtering. A platinum protective coating 14 was applied to the titanium adhesive layer 12 by sputtering. Scotch tape was applied to the tip 22 and the substrate 20 and then peeled off. The peeled Scotch tape did not contain either the protective coating 14 or / or the adhesive coating 12.

[0040] [Comparative Example 2] An interface cone 18 containing copper was used as the substrate material 20 and nickel as the chip material 22. A multilayer coating 10 was applied to at least one portion of the substrate 20 and chip 22. As shown in Figure 7A, the multilayer coating 10 contained 100 nm sputtered titanium (adhesive layer 12) and 1 μm sputtered platinum (protective coating 14). The interface cone 18 was operated in ICP-MS for 6 hours. A portion of the surface showed the color of copper. As shown in Figures 7B and 7C, scanning electron microscopy / energy dispersive spectroscopy (SEMS / EDS) analysis of the substrate 20 showed various copper nanostructures (e.g., evidence of copper ion diffusion).

[0041] [Comparative Example 3] An interface cone 18 containing copper as the substrate material 20 and nickel as the chip material 22 was used. As shown in Figure 8A, a multilayer coating 10 was applied to at least one portion of the substrate 20 and chip 22. The multilayer coating 10 contained 100 nm sputtered titanium (adhesive layer 12) and 1 μm sputtered platinum (protective coating 14). The multilayer coating 10 also contained a 500 nm sputtered nickel diffusion barrier layer 16 placed between the adhesive layer 12 and the protective layer 14. The interface cone 18 was operated in ICP-MS for 6 hours. Part of the surface showed the color of copper. As shown in Figures 8B and 8C, scanning electron microscopy / energy dispersive spectroscopy (SEMS / EDS) analysis of the substrate 20 showed various copper nanostructures.

[0042] [Example 2] An interface cone 18 containing copper as the substrate material 20 and nickel as the chip material 22 was used. A multilayer coating 10 was applied to at least one portion of the substrate 20 and chip 22. The multilayer coating 10 contained 100 nm sputtered titanium (adhesive layer 12) and 1 μm sputtered platinum (protective coating 14). The multilayer coating 10 also contained a 2-30 micrometer electroplated nickel diffusion barrier layer 16 placed between the adhesive layer 12 and the protective layer 14. The interface cone 18 was operated in ICP-MS for 30 hours. As shown in Figure 6, scanning electron microscopy / energy-dispersive spectroscopy (SEMS / EDS) analysis showed only the platinum layer.

[0043] [Example 3] Figure 9A shows an image of an interface cone 18 having a nickel tip 22 and a copper substrate 20. Figure 9B shows an interface cone 18 having a nickel tip 22 and a nickel-electroplated copper substrate 20. Figure 9C shows an interface cone 18 having a nickel tip 22 and a copper substrate 20 with a multilayer coating. The multilayer coating included a diffusion barrier layer, an adhesive layer, and a protective layer. Both titanium and platinum were sputter-coated at a ratio of 100 nm of titanium to 1 μm of platinum.

[0044] A composition containing 10% aqua regia (HCl:HNO3 in a 3:1 ratio) with 100 ppm Ca2+ was applied to each interface cone. The composition readily deposited on the interface cone 18, and repeated cleaning of the deposited Ca2+ ions and Ca salts caused deterioration of the cone surface. In this way, accelerated life testing was performed on each interface cone 18.

[0045] The interface cones were operated under ICP-MS for 10 hours with the composition remaining on each interface cone 18. The interface cones were examined by SEM / EDS. As shown in Figure 9A, the copper substrate corroded easily and contained flaky black deposits, which were determined to be nanostructures of copper oxide. The interface cones 18 with multilayer coatings (Figure 9C) appeared the cleanest. As mentioned above, reducing the need for cleaning the interface cones 18 further increased the lifespan of the interface cones 18 by avoiding improper cleaning and accidental damage during cleaning.

[0046] A method for manufacturing a coated interface cone includes preparing an interface cone having a substrate and a tip, depositing an adhesive layer on at least one portion of the substrate and the tip, and depositing a protective layer. This method is a method for depositing the protective layer by sputtering platinum or electroplating platinum. This method is a method for depositing the adhesive layer by sputtering. This method is a method in which the substrate is copper and further includes the step of depositing an adhesive layer after depositing a diffusion barrier layer. This method is a method in which the diffusion barrier layer is made of at least one material selected from electrolytic nickel, electroless nickel and combinations thereof.

[0047] As described above, those skilled in the art will recognize that these teachings can be implemented in various forms. Therefore, although these teachings have been described in relation to their specific embodiments and examples, the true scope of these teachings should not be limited. Various changes and modifications can be made as long as they do not deviate from the scope of the teachings herein.

[0048] The scope of this disclosure should be interpreted broadly. This disclosure is intended to disclose equivalents, means, systems, and methods for obtaining the devices, activities, and mechanical actions disclosed herein. With respect to each of the devices, articles, methods, means, mechanical elements, or mechanisms disclosed herein, this disclosure is also intended to encompass and teach equivalents, means, systems, and methods for practicing many of the embodiments, mechanisms, and devices disclosed herein. This disclosure also evaluates coatings and many of their embodiments, features, and elements. Such coatings may be dynamic in their use and operation, and this disclosure is intended to encompass equivalents, means, systems, and methods for the use of coatings and / or interface cones, as well as many of their embodiments consistent with the description and spirit of the operation and function disclosed herein. Similarly, the claims of this application should be interpreted broadly. The descriptions of the invention herein are essentially illustrative in many of their embodiments, and modifications that do not depart from the spirit of the invention are intended to be within the scope of the invention. Such modifications should not be considered to depart from the spirit and scope of the invention.

Claims

1. An adhesive layer made of at least one material selected from titanium, chromium, tungsten, or a combination thereof, A protective coating made from platinum A multilayer coating for interface cones, equipped with the features mentioned above.

2. The multilayer coating according to claim 1, wherein the interface cone transports ions from the plasma to a mass spectrometer.

3. The multilayer coating according to claim 1, wherein the protective coating is exposed to a corrosive acid at a temperature of 1000°C.

4. The multilayer coating according to claim 1, wherein the protective coating is insoluble in acids having a pH in the range of 1 to 7.

5. The multilayer coating according to claim 1, wherein the protective coating is a single layer of platinum with a thickness of 2 μm to 6 μm.

6. The multilayer coating according to claim 1, wherein the protective coating has a purity higher than 95%.

7. The multilayer coating according to claim 1, wherein the adhesive layer consists of two or more layers, and each layer is made of a different material.

8. The multilayer coating according to claim 1, wherein the adhesive layer has a thickness of 10 nm to 500 nm.

9. The multilayer coating according to claim 1, further comprising a diffusion barrier layer.

10. The multilayer coating according to claim 9, wherein the diffusion barrier layer is made of at least one material selected from electrolytic nickel, electroless nickel, or a combination thereof.

11. The multilayer coating according to claim 9, wherein the diffusion barrier layer is present in a thickness range greater than 500 nm.

12. Substrate and Tips and An interface cone comprising, An interface cone in which at least one portion of the substrate and the chip is coated with the multilayer coating described in claim 1.

13. The interface cone according to claim 12, wherein the substrate is made of at least one material selected from copper or nickel.

14. The interface cone according to claim 12, wherein the tip is made of at least one material selected from nickel or platinum.

15. The interface cone according to claim 12, wherein the substrate is copper, the chip is platinum, and the multilayer coating comprises a nickel diffusion barrier layer.

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