A method for depositing a nitride film on the surface of a glass bottle

Abstract

The application discloses a method for depositing nitride film on the surface of a glass bottle and belongs to the technical field of glass preparation. The method comprises the following steps: S1, plasma etching pretreatment, performing plasma etching on the inner surface of the glass bottle; S2, gradient transition layer deposition, depositing a nitride gradient transition layer on the pretreated surface by adopting a magnetron sputtering-ion plating technology; S3, functional layer deposition, depositing a nitride functional layer on the gradient transition layer; and S4, plasma post-treatment, performing plasma treatment on the deposited functional layer. The system process of the plasma etching pretreatment, the gradient transition layer deposition, the functional layer deposition and the plasma post-treatment effectively enhances the bonding force between the film layer and the glass substrate, alleviates the internal stress caused by the difference in the thermal expansion coefficient, and obtains the nitride functional layer which is compact in structure and few in defects.

Description

Technical Field

[0001] This invention belongs to the field of glass preparation technology, specifically, it relates to a method for depositing a nitride film on the surface of a glass bottle. Background Technology

[0002] Glass, with its excellent optical transparency, good mechanical strength, outstanding thermal stability, and chemical inertness, has long been considered an ideal material for pharmaceutical storage and transportation packaging. However, when containing pharmaceutical solutions, especially those with high or low pH values, the glass surface may experience varying degrees of corrosion, leading to the precipitation of metallic or non-metallic ions such as sodium, calcium, and silicon. This precipitation can form tiny particles or deposits, potentially altering the composition of the pharmaceutical solution, affecting its efficacy and safety, and may even clog precision drug delivery devices. Therefore, effectively inhibiting the precipitation of ions and particles from the glass surface is crucial for ensuring the stability of the pharmaceutical solution and the safety of medication use.

[0003] To improve the chemical resistance and barrier properties of glass containers, the industry has attempted to coat their surfaces with inorganic protective films, such as nitride films deposited using magnetron sputtering. However, these existing technologies still face significant challenges when applied to glass bottles, especially for modifying their inner surfaces. Due to the smoothness and high chemical inertness of glass surfaces, directly deposited films often lack adhesion and are prone to peeling under thermal or mechanical stress, failing to provide long-term reliable protection. Furthermore, for the inner surfaces of glass bottles with complex shapes and deep cavities, existing coating technologies struggle to ensure uniform film thickness and a dense structure; pores or defects in the film can severely weaken its barrier properties. In addition, if the internal stress generated during deposition is not effectively released, it can easily lead to microcracks in the film, affecting its integrity and durability. Some processes involving high temperatures may also cause thermal damage to the glass substrate, while low-temperature processes often fail to produce high-performance, dense films.

[0004] Therefore, existing methods are insufficient to form a high-performance nitride barrier film with strong adhesion, uniform density, low internal stress, and compatibility with the substrate on the inner surface of glass bottles. A new proprietary technology is urgently needed to solve these problems. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for depositing a nitride film on the surface of a glass bottle.

[0006] The objective of this invention can be achieved through the following technical solutions: A method for depositing a nitride film on the surface of a glass bottle includes the following steps: S1: Plasma etching pretreatment: Plasma etching is performed on the inner surface of the glass bottle; S2: Gradient transition layer deposition: A nitride gradient transition layer is deposited on the pretreated surface using magnetron sputtering-ion plating technology; S3: Functional layer deposition: A nitride functional layer is deposited on the gradient transition layer; S4: Plasma post-processing: Plasma treatment is performed on the deposited functional layer.

[0007] In a more optimized manner, the process parameters for plasma etching in step S1 are as follows: a mixed gas of Ar and O2 is used, the volume ratio of Ar to O2 is 3:1, the radio frequency power is 100-150W, the cavity pressure is 20-50Pa, the processing time is 5-10min, and the etching depth is 5-10nm.

[0008] In a more optimized manner, in step S2, the gradient transition layer is a TiN layer; wherein, the gradient transition layer deposition process is as follows: using a Ti target, under an N2 atmosphere, ion bombardment of 50-100 eV is applied, the N2 flow rate is 10-20 sccm, the substrate temperature is 150-200℃, the sputtering power is 200-300W, the bias voltage is -50 to -100V, and the deposition thickness is 5-10 nm.

[0009] In a more optimized manner, in step S3, the process for depositing the functional layer is as follows: using one of Si targets, TiAl targets, Zr targets or Cr targets, introducing a mixed gas of N2 and O2, with a radio frequency power of 300-500W, a pressure of 10-30Pa, a substrate rotation speed of 50-100rpm, and a deposition thickness of 50-200nm.

[0010] In a more optimized manner, in step S4, the plasma post-treatment process is as follows: using He plasma, with a processing power of 100W, a processing temperature of 150℃, and a processing time of 10-15min.

[0011] The beneficial effects of this invention are: This invention utilizes the synergistic effect of plasma etching and ion bombardment to construct a highly active interface and form chemical bonds on the glass surface, effectively solving the problem of poor adhesion of nitride films on smooth glass surfaces. Details are as follows: Firstly, the introduction of a gradient transition layer creates a gradual change in composition and performance between the glass substrate and the functional layer. This not only improves interfacial compatibility but also effectively buffers stress concentration caused by differences in thermal expansion coefficients, significantly enhancing the bonding stability and crack resistance of the composite film under temperature changes or mechanical loads.

[0012] Secondly, the magnetron sputtering-ion plating composite deposition technology used promotes the surface migration and rearrangement of atoms by continuously bombarding the growing film with controlled ions, and inhibits the formation of columnar crystal structures. This results in a nitride functional layer with fine grains, dense structure, and few defects, giving it excellent impermeability, chemical corrosion resistance, and good mechanical properties.

[0013] Thirdly, the entire process temperature is strictly controlled within the low-temperature range that the glass substrate can withstand, avoiding a decrease in substrate strength or deformation due to thermal stress, and fully preserving the original optical transparency and mechanical integrity of the glass. Simultaneously, by flexibly selecting target materials of different compositions and cooperating with corresponding reactive gases, this method can achieve controllable preparation of nitride film composition and function under the same process system, possessing both good process adaptability and functional expansion capabilities. Detailed Implementation

[0014] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0015] Example 1: A method for depositing a nitride film on the surface of a glass bottle, comprising the following steps: S1: Plasma etching pretreatment The glass bottle was fixed on a rotating support, and an Ar / O2 mixed gas (volume ratio 3:1) was introduced into the processing chamber to perform plasma etching on the inner surface of the glass bottle to form a nanoscale trench structure, thereby increasing the surface roughness Ra of the glass bottle to 0.5 nm and introducing hydroxyl active sites. The etching conditions were set as follows: RF power 100 W, pressure 20 Pa, etching time 5 min, and etching depth controlled at 5 nm. S2: Gradient transition layer deposition A magnetron sputtering-ion plating composite technology was used, with a Ti target of >99.95% purity as the target material, to deposit a TiN gradient transition layer on the surface of a pretreated glass bottle. Ion bombardment with an energy of 50eV was used to promote the bonding of Ti-O bonds with the glass surface. The thickness of the transition layer was 5nm. During the deposition process, N2 gas was introduced with a flow rate of 10sccm, and the substrate temperature was controlled at 150℃, the sputtering power at 200W, and the bias voltage at -50V. S3: Functional layer deposition By switching the target material to Si, SiN was deposited on the TiN gradient transition layer. xThe nitride functional layer has a thickness of 50 nm. During deposition, a N2 / O2 mixed gas (flow ratio 3:1) is introduced, and the RF power is set to 300 W, the pressure to 10 Pa, and the substrate rotation speed to 50 rpm. S4: Plasma Post-processing SiN x After the functional layer deposition is completed, He plasma is introduced into the processing chamber to perform post-processing on the functional layer to release the internal stress of the film and improve the film density. The post-processing conditions are: power 100W, temperature 150℃, processing time 10min, and the film density after processing is >98%.

[0016] Example 2: A method for depositing a nitride film on the surface of a glass bottle, comprising the following steps: S1: Plasma etching pretreatment The glass bottle was fixed on a rotating support, and an Ar / O2 mixed gas (volume ratio 3:1) was introduced into the processing chamber to perform plasma etching on the inner surface of the glass bottle to form a nanoscale trench structure, thereby increasing the surface roughness Ra of the glass bottle to 1 nm and introducing hydroxyl active sites. The etching conditions were set as follows: RF power 150 W, pressure 50 Pa, etching time 10 min, and etching depth controlled at 10 nm. S2: Gradient transition layer deposition A magnetron sputtering-ion plating composite technology was used, with a Ti target of >99.95% purity as the target material, to deposit a TiN gradient transition layer on the surface of a pretreated glass bottle. Ion bombardment with an energy of 100eV was used to promote the bonding of Ti-O bonds with the glass surface. The thickness of the transition layer was 10nm. During the deposition process, N2 gas was introduced with a flow rate of 20sccm, and the substrate temperature was controlled at 200℃, the sputtering power at 300W, and the bias voltage at -100V. S3: Functional layer deposition The target material was switched to TiAl target, and a TiAlN nitride functional layer was deposited on the TiN gradient transition layer. The thickness of the functional layer was 200nm. During deposition, a N2 / O2 mixed gas (flow ratio 5:1) was introduced, and the RF power was set to 500W, the pressure to 30Pa, and the substrate rotation speed to 100rpm. S4: Plasma Post-processing After the TiAlN functional layer is deposited, He plasma is introduced into the processing chamber to perform post-treatment on the functional layer to release the internal stress of the film and improve the film density. The post-treatment conditions are: power 100W, temperature 150℃, processing time 15min, and the film density after treatment is >98%.

[0017] Example 3: A method for depositing a nitride film on the surface of a glass bottle, comprising the following steps: S1: Plasma etching pretreatment The glass bottle was fixed on a rotating support, and an Ar / O2 mixed gas (volume ratio 3:1) was introduced into the processing chamber to perform plasma etching on the inner surface of the glass bottle to form a nanoscale trench structure, thereby increasing the surface roughness Ra of the glass bottle to 0.8 nm and introducing hydroxyl active sites. The etching conditions were set as follows: RF power 120 W, pressure 30 Pa, etching time 8 min, and etching depth controlled at 8 nm. S2: Gradient transition layer deposition A magnetron sputtering-ion plating composite technology was used, with a Ti target of >99.95% purity as the target material, to deposit a TiN gradient transition layer on the surface of a pretreated glass bottle. Ion bombardment with an energy of 70eV was used to promote the bonding of Ti-O bonds with the glass surface. The thickness of the transition layer was 8nm. During the deposition process, N2 gas was introduced with a flow rate of 15sccm, and the substrate temperature was controlled at 180℃, the sputtering power at 250W, and the bias voltage at -80V. S3: Functional layer deposition The target material was switched to Zr target, and a ZrN nitride functional layer was deposited on the TiN gradient transition layer. The thickness of the functional layer was 160nm. During deposition, a N2 / O2 mixed gas (flow ratio 4:1) was introduced, and the RF power was set to 400W, the pressure to 20Pa, and the substrate rotation speed to 80rpm. S4: Plasma Post-processing After the ZrN functional layer is deposited, He plasma is introduced into the processing chamber to perform post-processing on the functional layer to release the internal stress of the film and improve the film density. The post-processing conditions are: power 100W, temperature 150℃, processing time 12min, and the film density after processing is >98%.

[0018] Comparative Example 1: Blank glass bottle without nitride film deposition Testing and experimentation: The glass bottles with deposited films in Examples 1-3 and the blank glass bottle without nitride film in Comparative Example 1 were tested for temperature and acid / alkali resistance using the cross-cut adhesion test. The data are shown in the table below: Conclusion: Based on the technical solution and test results of the embodiments of this invention, this method effectively solves the problem of depositing high-performance nitride films on the smooth and chemically inert inner surface of glass bottles. Through a systematic process of plasma etching pretreatment, gradient transition layer deposition, functional layer deposition, and plasma post-treatment, the adhesion between the film and the glass substrate is effectively enhanced, internal stress caused by differences in thermal expansion coefficients is alleviated, and a dense nitride functional layer with few defects is obtained.

[0019] Experimental data show that glass bottles treated with this method did not exhibit film peeling or corrosion under harsh conditions such as high temperature, acid, and alkali resistance, significantly improving their chemical stability and barrier properties. In contrast, blank glass bottles without deposited film showed obvious corrosion and peeling under the same conditions. This method employs a low-temperature process throughout, avoiding thermal damage to the glass substrate and maintaining its original optical and mechanical properties. It possesses good process controllability and functional expansion potential, making it suitable for fields such as pharmaceutical packaging where high container cleanliness and chemical resistance are required.

[0020] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0021] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for depositing a nitride film on the surface of a glass bottle, characterized in that, Includes the following steps: S1: Plasma etching pretreatment: Plasma etching is performed on the inner surface of the glass bottle; S2: Gradient transition layer deposition: A nitride gradient transition layer is deposited on the pretreated surface using magnetron sputtering-ion plating technology; S3: Functional layer deposition: A nitride functional layer is deposited on the gradient transition layer; S4: Plasma post-processing: Plasma treatment is performed on the deposited functional layer.

2. The method for depositing a nitride film on the surface of a glass bottle according to claim 1, characterized in that, In step S1, the process parameters for plasma etching are as follows: a mixed gas of Ar and O2 is used, the volume ratio of Ar to O2 is 3:1, the radio frequency power is 100-150W, the cavity pressure is 20-50Pa, the processing time is 5-10min, and the etching depth is 5-10nm.

3. The method for depositing a nitride film on the surface of a glass bottle according to claim 1, characterized in that, In step S2, the gradient transition layer is a TiN layer; wherein, the gradient transition layer deposition process is as follows: using a Ti target, under a N2 atmosphere, ion bombardment of 50-100eV is applied, the N2 flow rate is 10-20sccm, the substrate temperature is 150-200℃, the sputtering power is 200-300W, the bias voltage is -50 to -100V, and the deposition thickness is 5-10nm.

4. The method for depositing a nitride film on the surface of a glass bottle according to claim 1, characterized in that, In step S3, the process for depositing the functional layer is as follows: using one of Si target, TiAl target, Zr target or Cr target, a mixed gas of N2 and O2 is introduced, the radio frequency power is 300-500W, the pressure is 10-30Pa, the substrate rotation speed is 50-100rpm, and the deposition thickness is 50-200nm.

5. The method for depositing a nitride film on the surface of a glass bottle according to claim 4, characterized in that, The flow ratio of N2 to O2 is 3:1-5:

1.

6. The method for depositing a nitride film on the surface of a glass bottle according to claim 1, characterized in that, In step S4, the plasma post-treatment process is as follows: He plasma is used, the processing power is 100W, the processing temperature is 150℃, and the processing time is 10-15min.

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