A method for depositing and growing a ruthenium film on a surface of a glass substrate

Abstract

The application relates to the technical field of thin film materials, in particular to a method for depositing and growing a ruthenium thin film on the surface of a glass substrate; the method comprises the following steps: pretreating a glass substrate to obtain a pretreated substrate; under the condition of an inert atmosphere, using a ruthenium source of tricarbonylruthenium to perform first atomic layer deposition treatment on the pretreated substrate to obtain a rough ruthenium thin film substrate containing tricarbonyl; using an oxygen source to perform second atomic layer deposition treatment on the rough ruthenium thin film substrate, so that the tricarbonyl of the rough ruthenium thin film substrate undergoes a redox reaction, and the rough ruthenium thin film substrate is removed to obtain a glass substrate containing a ruthenium thin film. The method successfully realizes the target of depositing and growing a high-quality ruthenium thin film on the surface of a glass substrate by the ingenious combination of twice atomic layer deposition treatment and a redox reaction. The method not only improves the purity and uniformity of the ruthenium thin film, so that the non-uniformity of the ruthenium thin film is controlled below 0.35%, but also significantly enhances the bonding force and stability of the ruthenium thin film and the glass substrate.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of thin film materials, and in particular to a method for depositing and growing a ruthenium thin film on a glass substrate. BACKGROUND

[0002] In the manufacturing process of modern electronic and optoelectronic devices, metal thin films are widely used due to their unique electrical, thermal and optical properties. Ruthenium (Ru) thin films have become the preferred material for integrated circuit interconnection technology due to their high electrical conductivity and good thermal stability. At present, glass is mostly used as a substrate in the microelectronic and optoelectronic fields, and then a layer of ruthenium thin film is deposited on the surface of the glass substrate. Then, according to the formed ruthenium film, devices related to the modern electronic and optoelectronic fields are prepared.

[0003] At present, the techniques for depositing ruthenium thin films on glass substrates include physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques. However, these deposition techniques have some limitations when depositing ruthenium thin films, such as difficulty in accurately controlling the thickness and uniformity of the growth of ruthenium thin films, resulting in poor quality of the ruthenium thin films. SUMMARY

[0004] The present application provides a method for depositing and growing a ruthenium thin film on a glass substrate, to solve the technical problem of how to improve the quality of the ruthenium thin film deposited on the surface of the glass substrate.

[0005] In a first aspect, the embodiments of the present application provide a method for depositing and growing a ruthenium thin film on a glass substrate, which comprises:

[0006] pre-treating a glass substrate to obtain a pre-treated substrate;

[0007] performing a first atomic layer deposition treatment on the pre-treated substrate using a ruthenium source of tricarbonylruthenium in an inert atmosphere to obtain a rough ruthenium thin film substrate containing tricarbonyl;

[0008] performing a second atomic layer deposition treatment on the rough ruthenium thin film substrate containing tricarbonyl using an oxygen source to cause a redox reaction of the tricarbonyl in the rough ruthenium thin film substrate and remove the rough ruthenium thin film substrate, thereby obtaining a glass substrate containing a ruthenium thin film.

[0009] Optionally, the first atomic layer deposition treatment comprises a first heating section and a tricarbonylruthenium ruthenium source pulse section, the end point temperature of the first heating section is 150-200℃, and the pulse time of the tricarbonylruthenium ruthenium source pulse section is 0.1-5.0s.

[0010] Optionally, the first atomic layer deposition process further comprises a first carrier gas purging section, the first carrier gas purging section has a time of 0.1s-5s, the first carrier gas purging section has a temperature of 95℃-105℃, and the first carrier gas purging section has a carrier gas flow rate of 10sccm-150sccm.

[0011] Optionally, the second atomic layer deposition process comprises a second heating section and an oxygen source pulse section, the second heating section has a final temperature of 150℃-200℃, and the oxygen source pulse section has a pulse time of 0.1s-1.0s.

[0012] Optionally, the second atomic layer deposition process further comprises a second carrier gas purging section, the second carrier gas purging section has a time of 0.01s-0.05s, the second carrier gas purging section has a temperature of 95℃-105℃, and the second carrier gas purging section has a carrier gas flow rate of 10sccm-150sccm.

[0013] Optionally, the temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process is 0.05torr-0.40torr.

[0014] Optionally, the ruthenium source of the ruthenium tricarbonyl type has a temperature of 40℃-50℃; and / or

[0015] The oxygen source has a temperature of 15℃-30℃.

[0016] Optionally, the type of the ruthenium source of the ruthenium tricarbonyl type comprises at least one of (η4-2,3-dimethylbut-1,3-diene)tricarbonylruthenium, (η4-but-1,3-diene)tricarbonylruthenium, (1,3-cyclohexadienyl)tricarbonylruthenium, (η4-2-methylbut-1,3-diene)tricarbonylruthenium, and dodecacarbonyltriruthenium; and / or

[0017] The type of the oxygen source comprises oxygen and / or water.

[0018] Optionally, the pretreatment of the glass substrate to obtain a pretreated substrate comprises the following steps:

[0019] Mixing anhydrous ethanol and part of deionized water to obtain a mixed solution;

[0020] Soaking the glass substrate in the mixed solution and performing a first ultrasonic treatment to obtain a first cleaned substrate;

[0021] Soaking the first cleaned substrate in the remaining deionized water and performing a second ultrasonic treatment to obtain a second cleaned substrate;

[0022] Drying the second cleaned substrate using an inert gas to obtain a pretreated substrate;

[0023] The first ultrasonic time is greater than or equal to 30 minutes, and the second ultrasonic time is greater than or equal to 15 minutes.

[0024] Optionally, the glass substrate comprises a BF33 type glass substrate.

[0025] Compared with the prior art, the above technical solution provided by the embodiments of the present application has the following advantages:

[0026] The method for depositing and growing a ruthenium thin film on a glass substrate surface provided by the embodiments of the present application first pretreats the glass substrate to remove surface contaminants on the glass substrate, then deposits ruthenium atoms of a ruthenium source of tricarbonylruthenium in a layered structure on the surface of the glass substrate through a first atomic layer deposition process to preliminarily form a rough ruthenium thin film substrate containing tricarbonyl with uniform thickness, and then oxidizes the tricarbonyl of the rough ruthenium thin film substrate into carbon-containing gas by taking an oxygen source as an oxidizing agent through a second atomic layer deposition process, so that the tricarbonyl is removed from the ruthenium thin film substrate, and the rough ruthenium thin film is uniformly grown to form a ruthenium thin film, so that a pure ruthenium thin film is deposited on the surface of the glass substrate. In addition, the introduction of the oxygen source can also increase the nucleation density of the ruthenium thin film, adjust and optimize the growth kinetics of the conversion of ruthenium ions into ruthenium atoms, and the surface energy between the glass substrate and the ruthenium thin film, so that the rough ruthenium thin film is further uniformly grown to form a ruthenium thin film, and the uniform distribution of the ruthenium thin film can further improve the quality of the ruthenium thin film deposited on the surface of the glass substrate. Therefore, the method can effectively improve the quality of the ruthenium thin film deposited on the surface of the glass substrate through the two atomic layer deposition processes and the redox reaction. BRIEF DESCRIPTION OF DRAWINGS

[0027] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the application.

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the accompanying drawings needed to be used in the embodiments or the prior art description will be briefly introduced. Obviously, other drawings can also be obtained by those skilled in the art without any creative labor based on these drawings.

[0029] Figure 1 A method flow diagram for depositing and growing a ruthenium thin film on a glass substrate surface is provided for the embodiments of the present application.

[0030] Figure 2 A detailed flow diagram of a method for depositing and growing a ruthenium thin film on a glass substrate surface is provided for the embodiments of the present application.

[0031] Figure 3Figure showing surface characteristics of the glass substrate containing the ruthenium thin film provided in Example 1 of the present application; Figure 3 (a) is a scanning electron microscope result of the surface of the ruthenium thin film at a scale of 100 nm, Figure 3 (b) is a scanning electron microscope result of the surface of the ruthenium thin film at a scale of 200 nm, Figure 3 (c) is a scanning electron microscope result of the cross section of the ruthenium thin film at a scale of 100 nm of two sampling points selected,

[0032] Figure 4 Figure showing EDS detection result of the glass substrate containing the ruthenium thin film provided in Example 1 of the present application; wherein, Figure 4 (a) is a layered image of EDS of the ruthenium thin film, Figure 4 (b) is a surface scanning analysis result of the ruthenium element of the ruthenium thin film, Figure 4 (c) is a surface scanning analysis result of the oxygen element of the ruthenium thin film, Figure 4 (d) is a surface scanning analysis result of the silicon element of the ruthenium thin film;

[0033] Figure 5 Figure showing the principle flow chart of the method for depositing and growing the ruthenium thin film on the surface of the glass substrate provided in the present application. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work shall fall within the scope of protection of the present application.

[0035] The various embodiments of the present application can exist in the form of a range; it should be understood that the description in the form of a range is merely for the convenience and brevity, and should not be understood as a hard limitation on the scope of the present application; therefore, it should be considered that the described range has specifically disclosed all possible sub-ranges and single values within the range; for example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, regardless of the range; in addition, whenever a numerical range is indicated in the present text, it means that any cited number (fraction or integer) within the indicated range is included.

[0036] In this document, the terms "comprise" and "comprising" refer to "including without limitation." The relational terms such as "first" and "second" and the like can merely be used to differentiate one entity or action from another, and do not necessarily require or imply any actual relationship or order between or among the entities or actions. The term "and / or" describes association between associated objects, and means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone; wherein A and B can be singular or plural. "At least one" means one or more, and "multiple" means two or more; "at least one" or "at least one of the following" or the like means any combination of the items, including a single item or a combination of multiple items; for example, "at least one of a, b, or c" or "at least one of a, b, and c" can mean a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be singular or plural. The "parts ratio" such as weight parts, mass parts, etc. represents the proportional relationship between components. In the proportional relationship described herein, the parameters that need to be described by the proportion should be understood as the front item of the proportional formula in the order of description, and the proportional number should be understood as the latter item of the proportional formula, for example, the mass ratio of substance A, substance B, and substance C is 1:2:3, then substance A, substance B, and substance C should be one-to-one corresponding in the proportional formula according to the description order, i.e., the mass of substance A: the mass of substance B: the mass of substance C = 1:2:3.

[0037] Unless otherwise specifically noted, the various raw materials, reagents, instruments and equipment used in this document can be purchased on the market or can be prepared by existing methods.

[0038] Unless otherwise specifically noted, the various raw materials, reagents, instruments and equipment used in this document can be purchased on the market or can be prepared by existing methods.

[0039] Figure 1 An exemplary flowchart of a method for depositing and growing a ruthenium thin film on a glass substrate surface is shown;

[0040] Figure 5 An exemplary principle flowchart of a method for depositing and growing a ruthenium thin film on a glass substrate surface is shown;

[0041] As shown in Figure 1 and Figure 5 A method for depositing and growing a ruthenium thin film on a glass substrate surface is provided, which comprises:

[0042] S1. Pre-treat the glass substrate to obtain a pre-treated substrate;

[0043] S2. Perform a first atomic layer deposition treatment on the pre-treated substrate using a ruthenium source of tricarbonylruthenium under an inert atmosphere to obtain a tricarbonyl-containing rough ruthenium film substrate;

[0044] S3. Perform a second atomic layer deposition treatment on the tricarbonyl-containing rough ruthenium film substrate using an oxygen source to cause a redox reaction of the tricarbonyl of the rough ruthenium film substrate and remove the rough ruthenium film substrate to obtain a glass substrate containing a ruthenium film.

[0045] It should be noted that after pre-treatment, the glass substrate is free of impurities on its surface, which can increase the bonding sites of ruthenium atoms and the glass substrate in the subsequent first atomic layer deposition treatment stage, so that a rough ruthenium film can be initially grown on the surface of the glass substrate.

[0046] It should be noted that the method for depositing and growing a ruthenium film on the surface of a glass substrate provided by the embodiments of the present application is not only rigorous but also efficient, and the specific steps and principles are as follows:

[0047] (1) First, the glass substrate is subjected to strict pre-treatment. This step is crucial, and its purpose is to completely remove various contaminants that may exist on the surface of the glass substrate, such as dust, grease, organic residues, etc., thereby providing a clean and pollution-free surface environment for the subsequent deposition process. Pre-treatment usually includes cleaning, drying, and necessary surface activation treatment to ensure the best state of the glass substrate.

[0048] (2) Next, a first atomic layer deposition treatment is performed. In this stage, a tricarbonylruthenium source is selected as the deposition material. By precisely controlling the deposition conditions such as temperature, pressure, gas flow, etc., the ruthenium atoms in the tricarbonylruthenium are uniformly deposited on the surface of the pre-treated glass substrate in a layered structure. This process initially forms a rough ruthenium film substrate containing tricarbonyl with uniform thickness. Although this rough ruthenium film initially covers ruthenium, its purity and structure still need to be further optimized due to the presence of tricarbonyl.

[0049] (3) Subsequently, a second atomic layer deposition treatment stage is entered. In this stage, an oxygen source is introduced as an oxidizing agent. The introduction of the oxygen source has multiple effects: on the one hand, it can cause the tricarbonyl in the rough ruthenium film substrate to be oxidized into carbon-containing gases, which are then discharged from the deposition system, thereby achieving effective removal of tricarbonyl from the ruthenium film substrate; on the other hand, the presence of the oxygen source can also promote the further deposition and growth of ruthenium atoms, making the rough ruthenium film gradually uniform and dense during the oxidation process, and ultimately forming a high-quality ruthenium film.

[0050] Notably, the introduction of the oxygen source not only serves to remove the tricarbonyl group, but also positively influences the growth of the ruthenium thin film in multiple aspects. First, the oxygen source can increase the nucleation density of the ruthenium thin film, making the distribution of ruthenium atoms on the surface of the glass substrate more intensive and uniform. Second, the oxygen source can adjust and optimize the growth kinetics process of the conversion of ruthenium ions into ruthenium atoms, making the deposition process more stable and controllable. Finally, the oxygen source can also change the surface energy between the glass substrate and the ruthenium thin film, further enhancing the bonding force and stability between the ruthenium thin film and the glass substrate.

[0051] In summary, the embodiments of the present application successfully achieve the goal of depositing and growing high-quality ruthenium thin films on the surface of a glass substrate through the ingenious combination of two atomic layer deposition processes and redox reactions. This method not only improves the purity and uniformity of the ruthenium thin film, but also significantly enhances its bonding force and stability with the glass substrate, providing strong support for related field applications.

[0052] In some optional embodiments, the first atomic layer deposition process includes a first heating segment and a tricarbonyl ruthenium ruthenium source pulse segment, the end point temperature of the first heating segment is 150-200°C, and the pulse time of the tricarbonyl ruthenium ruthenium source pulse segment is 0.1-5.0s.

[0053] In these embodiments, the first atomic layer deposition process can include a first heating segment and a tricarbonyl ruthenium ruthenium source pulse segment, and the end point temperature of the first heating segment can be 150-200°C, and the pulse time of the tricarbonyl ruthenium ruthenium source pulse segment can be 0.1-5.0s, which promotes the uniform deposition of ruthenium atoms in a layered structure on the surface of the glass substrate during the first atomic layer deposition process, to preliminarily form a rough ruthenium thin film with uniform thickness.

[0054] The end point temperature of the first heating segment can be 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C.

[0055] The pulse time of the tricarbonyl ruthenium ruthenium source pulse segment can be 0.1s, 0.2s, 0.3s, 0.4s, 0.5s, 1.0s, 2.0s, 3.0s, 4.0s, or 5.0s.

[0056] In some optional embodiments, the first atomic layer deposition process further includes a first carrier gas purge segment, the time of the first carrier gas purge segment is 0.1-5s, the temperature of the first carrier gas purge segment is 95-105°C, and the carrier gas flow rate of the first carrier gas purge segment is 10-150sccm.

[0057] In these embodiments, the first atomic layer deposition process can further comprise a first carrier gas purge section, and the first carrier gas purge section can have a time of 0.1s to 5s, and the first carrier gas purge section can have a temperature of 95℃ to 105℃, and the first carrier gas purge section can have a carrier gas flow rate of 10sccm to 150sccm, so as to facilitate the first atomic layer deposition process to sufficiently blow out the residual ruthenium atoms and the unreacted ruthenium tricarbonyl ruthenium source in the atomic layer deposition processing equipment through the first carrier gas purge section, to facilitate the subsequent second atomic layer deposition process, and to obtain a ruthenium thin film with uniform thickness distribution.

[0058] The first carrier gas purge section can have a time of 0.1s, 0.2s, 0.3s, 0.4s, 0.5s, 1.0s, 2.0s, 3.0s, 4.0s, 5.0s, 10.0s, 15.0s, or 20.0s.

[0059] The first carrier gas purge section can have a temperature of 95℃, 96℃, 97℃, 98℃, 99℃, 100℃, 101℃, 102℃, 103℃, 104℃, or 105℃.

[0060] The first carrier gas purge section can have a carrier gas flow rate of 10sccm, 20sccm, 30sccm, 40sccm, 50sccm, 60sccm, 70sccm, 80sccm, 90sccm, 100sccm, 110sccm, 120sccm, 130sccm, 140sccm, or 150sccm.

[0061] In some optional embodiments, the second atomic layer deposition process comprises a second heating section and an oxygen source pulse section, the second heating section has an end point temperature of 150℃ to 200℃, and the oxygen source pulse section has a pulse time of 0.01s to 1.0s.

[0062] In these embodiments, the second atomic layer deposition process can comprise a second heating section and an oxygen source pulse section, and the second heating section can have an end point temperature of 150℃ to 200℃, and the oxygen source pulse section can have a pulse time of 0.01s to 10.0s, so as to facilitate the second atomic layer deposition process to oxidize the ruthenium tricarbonyl in the coarse ruthenium thin film into carbon-containing gas (carbon monoxide or carbon dioxide) under the oxidation condition of the oxygen source, so that the coarse ruthenium thin film is uniformly grown to form a high-purity ruthenium thin film, and the ruthenium thin film is uniformly deposited on the surface of the glass substrate.

[0063] The second heating section can have an end point temperature of 150℃, 160℃, 170℃, 180℃, 190℃, or 200℃.

[0064] The pulse time of the oxygen source pulse section can be 0.01 s, 0.05 s, 0.06 s, 0.07 s, 0.08 s, 0.09 s, or 0.10 s.

[0065] In some alternative embodiments, the second atomic layer deposition process further comprises a second carrier gas purge section, the second carrier gas purge section has a time of 0.01 s to 0.05 s, the second carrier gas purge section has a temperature of 95 °C to 105 °C, and the second carrier gas purge section has a carrier gas flow rate of 10 sccm to 150 sccm.

[0066] In these embodiments, the second atomic layer deposition process can further comprise a second carrier gas purge section, and the second carrier gas purge section can have a time of 0.01 s to 0.05 s, and the second carrier gas purge section can have a temperature of 95 °C to 105 °C, and the second carrier gas purge section can have a carrier gas flow rate of 10 sccm to 150 sccm, so that the residual oxygen source of the second atomic layer deposition process is sufficiently purged out of the atomic layer deposition equipment for facilitating the subsequent atomic layer deposition process in the cycle stage, and a ruthenium thin film with uniform thickness distribution is obtained.

[0067] The second carrier gas purge section can have a time of 0.01 s, 0.02 s, 0.03 s, 0.04 s, or 0.05 s.

[0068] The second carrier gas purge section can have a temperature of 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, or 105 °C.

[0069] The second carrier gas purge section can have a carrier gas flow rate of 10 sccm, 20 sccm, 30 sccm, 40 sccm, 50 sccm, 60 sccm, 70 sccm, 80 sccm, 90 sccm, 100 sccm, 110 sccm, 120 sccm, 130 sccm, 140 sccm, or 150 sccm.

[0070] In some alternative embodiments, the temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process is 0.05 torr to 0.40 torr.

[0071] In these embodiments, the temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process can be 0.05 torr to 0.40 torr, so that the first atomic layer deposition process and the second atomic layer deposition process are sufficiently performed, and a ruthenium thin film with sufficient thickness and uniform distribution can be formed on the glass substrate.

[0072] The temperature offset value for the first atomic layer deposition process and the second atomic layer deposition process can be 0.05 torr, 0.06 torr, 0.07 torr, 0.08 torr, 0.09 torr, 0.10 torr, 0.20 torr, 0.30 torr, or 0.40 torr.

[0073] In some alternative embodiments, the ruthenium source of ruthenium tricarbonyl has a temperature of 40 °C to 50 °C; and / or

[0074] The oxygen source has a temperature of 15 °C to 30 °C.

[0075] In these embodiments, the ruthenium source of ruthenium tricarbonyl can have a temperature of 40 °C to 50 °C, which facilitates the temperature of the ruthenium source of ruthenium tricarbonyl for the first atomic layer deposition process to be within a suitable range to facilitate the first atomic layer deposition process to proceed sufficiently to obtain a rough ruthenium film of sufficient thickness and uniformity; and the oxygen source can have a temperature of 15 °C to 30 °C, which facilitates the temperature of the oxygen source for the second atomic layer deposition process to be within a suitable range to facilitate the second atomic layer deposition process to proceed sufficiently to obtain a ruthenium film of sufficient thickness and uniformity.

[0076] The ruthenium source of ruthenium tricarbonyl can have a temperature of 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, 46 °C, 47 °C, 48 °C, 49 °C, or 50 °C.

[0077] The oxygen source can have a temperature of 15 °C, 16 °C, 17 °C, 18 °C, 19 °C, 20 °C, 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, or 30 °C.

[0078] In some alternative embodiments, the ruthenium source of ruthenium tricarbonyl includes at least one of (η4-2,3-dimethylbut-1,3-diene)tricarbonylruthenium, (η4-but-1,3-diene)tricarbonylruthenium, (1,3-cyclohexadienyl)tricarbonylruthenium, (η4-2-methylbut-1,3-diene)tricarbonylruthenium, and dodecacarbonyltriruthenium; and / or

[0079] The oxygen source includes oxygen and / or water.

[0080] In these embodiments, the species of the tricarbonylruthenium ruthenium source can include at least one of (η4-2,3-dimethylbut-1,3-diene)tricarbonylruthenium, (η4-but-1,3-diene)tricarbonylruthenium, (1,3-cyclohexadienyl)tricarbonylruthenium, (η4-2-methylbut-1,3-diene)tricarbonylruthenium and dodecacarbonyltriruthenium, which can cover most of the tricarbonylruthenium ruthenium sources for atomic layer deposition processing to form a rough ruthenium film with sufficient thickness and uniform dispersion during the first atomic layer deposition processing; in addition, the species of the oxygen source includes oxygen and / or water, which can cover most of the oxygen sources for atomic layer deposition processing, and these oxygen sources can oxidize the tricarbonyl of the rough ruthenium film into carbon-containing gas as an oxidizing agent, so that the rough ruthenium film grows uniformly to form a pure ruthenium film and the ruthenium film is deposited on the surface of the glass substrate; in addition, these oxygen sources can also increase the nucleation density of the ruthenium film, adjust and optimize the growth kinetics of the conversion of ruthenium ions into ruthenium atoms, and the surface energy between the glass substrate and the ruthenium film, so that the rough ruthenium film further grows uniformly to form a ruthenium film, and further improves the uniformity of the distribution of ruthenium atoms on the surface of the glass substrate.

[0081] Figure 2 An example of a detailed flowchart of a method for depositing and growing a ruthenium film on a glass substrate surface is shown.

[0082] In some optional embodiments, as shown in Figure 2 The pre-treatment of the glass substrate to obtain a pre-treated substrate includes the following steps:

[0083] S101. Mixing anhydrous ethanol and part of deionized water to obtain a mixed solution;

[0084] S102. Immersing the glass substrate in the mixed solution and performing first ultrasonic treatment to obtain a first cleaned substrate;

[0085] S103. Immersing the first cleaned substrate in the remaining deionized water and performing second ultrasonic treatment to obtain a second cleaned substrate;

[0086] S104. Drying the second cleaned substrate with inert gas to obtain a pre-treated substrate;

[0087] The time of the first ultrasonic treatment is ≥ 30 min, and the time of the second ultrasonic treatment is ≥ 15 min.

[0088] In these embodiments, the cleaning solution is formed by mixing anhydrous ethanol and deionized water, and then the first ultrasonic treatment is used, which can effectively remove the organic and inorganic impurities of the glass substrate, so that a pure first cleaned substrate can be obtained; in addition, the deionized water is used as the cleaning solution and the second ultrasonic treatment is performed, which can further remove the components of the mixed solution and other impurities, so that a pure second cleaned substrate can be obtained.

[0089] It should be noted that the frequencies of the first and second ultrasonic waves can be the same, and the frequency used is a common frequency of existing ultrasonic cleaning.

[0090] It should be noted that the inert gas can be nitrogen or a zero-group element gas; and the drying method can be air drying.

[0091] In some optional embodiments, the glass substrate comprises a BF33 type glass substrate.

[0092] In these embodiments, the glass substrate can comprise a BF33 type glass substrate, which is a high borosilicate glass produced by Corning Incorporated, and has a relatively smooth plane and more binding sites as a glass substrate, so as to facilitate the deposition of ruthenium atoms of the tricarbonyl ruthenium type ruthenium source on the surface of the glass substrate and form a coarse ruthenium thin film.

[0093] The present application will be further described in conjunction with specific examples. The experimental methods in the following examples are not specified, and are generally determined according to national standards / industry standards; if there is no corresponding national standard / industry standard, the general international standard, conventional conditions or the conditions suggested by the manufacturer are used.

[0094] Example 1

[0095] As shown in Figure 2 and Figure 5 , a method for depositing and growing a ruthenium thin film on the surface of a glass substrate, comprising:

[0096] S101. Mixing anhydrous ethanol and part of deionized water in a mass ratio of 1:1 to obtain a mixed solution;

[0097] S102. Completely immersing a BF33 type glass substrate of Corning Incorporated in the mixed solution, and performing first ultrasonic wave to remove impurities and contaminants on the surface of the glass substrate to obtain a first cleaned substrate;

[0098] S103. Completely immersing the first cleaned substrate in the remaining deionized water, and performing second ultrasonic wave to obtain a second cleaned substrate;

[0099] S104. Blowing dry the second cleaned substrate using nitrogen to obtain a pretreated substrate;

[0100] The time of the first ultrasonic wave is 30 min, and the time of the second ultrasonic wave is 15 min.

[0101] The temperature of the heater section of the atomic layer deposition reaction chamber is set to 200℃, and then the temperature of the precursor (TOP) of the atomic layer deposition reaction chamber is kept consistent with the temperature of the heater;

[0102] S2. Introduce a tricarbonylruthenium ruthenium source into the atomic layer deposition reaction chamber, and use the tricarbonylruthenium ruthenium source to perform a first atomic layer deposition treatment on the pretreated substrate under an inert gas atmosphere, to obtain a rough substrate containing a rough ruthenium film;

[0103] S3. Introduce an oxygen source into the atomic layer deposition reaction chamber, and use the oxygen source to perform a second atomic layer deposition treatment on the rough substrate containing the rough ruthenium film under an inert gas atmosphere, so that the rough ruthenium film undergoes a reduction reaction, to obtain a glass substrate containing a ruthenium film.

[0104] According to the thickness of the ruthenium film required, the above-mentioned cycle process of the first atomic layer deposition treatment and the second atomic layer deposition treatment is repeated. Each cycle deposits one or more layers of metal atoms on the glass substrate, so that by accurately controlling the number of cycles, the thickness of the ruthenium film is accurately controlled. The total number of cycles of the first atomic layer deposition treatment and the second atomic layer deposition treatment is 100, and the growth rate of the ruthenium film in each cycle is 2.128 angstroms per cycle.

[0105] The first atomic layer deposition treatment includes a first heating section and a tricarbonylruthenium ruthenium source pulse section, the end temperature of the first heating section is 200℃, and the pulse time of the tricarbonylruthenium ruthenium source pulse section is 5.0s.

[0106] The first atomic layer deposition treatment further includes a first carrier gas purge section, the time of the first carrier gas purge section is 2s, the temperature of the first carrier gas purge section is 100℃, and the carrier gas flow rate of the first carrier gas purge section is 15sccm.

[0107] The second atomic layer deposition treatment includes a second heating section and an oxygen source pulse section, the end temperature of the second heating section is 200℃, and the pulse time of the oxygen source pulse section is 0.2s.

[0108] The second atomic layer deposition treatment further includes a second carrier gas purge section, the time of the second carrier gas purge section is 0.02s, the temperature of the second carrier gas purge section is 100℃, and the carrier gas flow rate of the second carrier gas purge section is 15sccm.

[0109] The temperature compensation value of the first atomic layer deposition treatment and the second atomic layer deposition treatment is 0.10torr.

[0110] The temperature of the tricarbonylruthenium ruthenium source is 48℃;

[0111] The temperature of the oxygen source is 25℃.

[0112] The type of ruthenium source of tricarbonylruthenium is (η4-2, 3-dimethylbut-1, 3-diene) tricarbonylruthenium (RuDMBDCO3) ;

[0113] The type of oxygen source is water.

[0114] Example 2

[0115] On the basis of the disclosure of Example 1, the following modifications are further made:

[0116] The end point temperature of the first heating section is 150℃, and the pulse time of the tricarbonylruthenium ruthenium source pulse section is 0.1s.

[0117] The time of the first carrier gas purge section is 1s, the temperature of the first carrier gas purge section is 95℃, and the carrier gas flow rate of the first carrier gas purge section is 20sccm.

[0118] The end point temperature of the second heating section is 150℃, and the pulse time of the oxygen source pulse section is 1.0s.

[0119] The time of the second carrier gas purge section is 0.01s, the temperature of the second carrier gas purge section is 95℃, and the carrier gas flow rate of the second carrier gas purge section is 20sccm.

[0120] The temperature compensation value of the first atomic layer deposition treatment and the second atomic layer deposition treatment is 0.05torr.

[0121] The temperature of the tricarbonylruthenium ruthenium source is 40℃;

[0122] The temperature of the oxygen source is 20℃.

[0123] Example 3

[0124] On the basis of the disclosure of Example 1, the following modifications are further made:

[0125] The end point temperature of the first heating section is 175℃, and the pulse time of the tricarbonylruthenium ruthenium source pulse section is 5.0s.

[0126] The time of the first carrier gas purge section is 5s, the temperature of the first carrier gas purge section is 105℃, and the carrier gas flow rate of the first carrier gas purge section is 100sccm.

[0127] The end point temperature of the second heating section is 175℃, and the pulse time of the oxygen source pulse section is 10.0s.

[0128] The time of the second carrier gas purge section is 0.05s, the temperature of the second carrier gas purge section is 105℃, and the carrier gas flow rate of the second carrier gas purge section is 100sccm.

[0129] The temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process is 0.40 torr.

[0130] The temperature of the ruthenium source is 50℃.

[0131] The temperature of the oxygen source is 30℃.

[0132] Comparative Example 1

[0133] Based on the disclosure of Example 1, the following modifications are further made:

[0134] A ruthenium thin film with the same thickness is formed using a conventional physical vapor deposition method.

[0135] Comparative Example 2

[0136] Based on the disclosure of Example 1, the following modifications are further made:

[0137] A ruthenium thin film with the same thickness is formed using a conventional chemical vapor deposition method.

[0138] Related experiments and effect data:

[0139] The glass substrate sample containing a ruthenium thin film obtained in Example 1 is selected at three sampling points, respectively, and the distribution of the ruthenium film thickness is counted, wherein the characterization of the ruthenium thin film surface and cross section of a certain area is as shown in Figure 3 , and the detection result of EDS is as shown in Figure 4 , the ruthenium film thickness of the two sampling points is 21.35 nm and 21.21 nm, respectively, and the non-uniformity is calculated to be 0.329%. According to this process, the glass substrate sample containing a ruthenium thin film of each example and comparative example is sampled and the non-uniformity is calculated, and the results are shown in Table 1. The calculation formula is: non-uniformity coefficient w=(ruthenium thin film thickness maximum-ruthenium thin film thickness minimum) / (ruthenium film thickness maximum+ruthenium film thickness minimum).

[0140] Table 1: Non-uniformity results of glass substrate samples containing ruthenium thin films of each example and comparative example

[0141]

[0142]

[0143] As can be seen from Table 1, the method for depositing and growing a ruthenium thin film on the surface of a glass substrate provided by the embodiments of the present application successfully achieves the goal of depositing and growing a high-quality ruthenium thin film on the surface of a glass substrate by the ingenious combination of twice atomic layer deposition treatment and redox reaction. This method not only improves the purity and uniformity of the ruthenium thin film, but also significantly enhances its adhesion and stability to the glass substrate, providing strong support for related applications, making the non-uniformity of the ruthenium thin film controlled below 0.35%, and providing a new technical approach and solution for the development of related fields.

[0144] In addition, the method for depositing and growing a ruthenium thin film on the surface of a glass substrate provided by the embodiments of the present application also has the following characteristics:

[0145] 1. Innovative application of substrate materials: Traditional atomic deposition treatment technology is mainly applied to semiconductor materials such as silicon wafers, while the method of the present application successfully deposits a ruthenium thin film on a glass substrate, which widens the application field of atomic deposition treatment technology and provides new possibilities for the application of glass materials in the field of electronics and optoelectronics.

[0146] 2. Use of new precursor source: The method uses a new type of precursor source for the deposition of a ruthenium thin film, which may bring higher reactivity and selectivity, improve the quality and performance of the thin film, reduce side reactions and waste generation, and improve the environmental friendliness and economic efficiency of the process.

[0147] 3. Potential improvement of thin film performance: The ruthenium thin film deposited on the glass substrate by the method through atomic deposition treatment has excellent electrical conductivity, thermal stability and catalytic activity due to the high uniformity and precise thickness control of atomic deposition treatment, which is crucial for improving the performance of related devices.

[0148] 4. Enhancement of process flexibility and controllability: The method can precisely control the thickness and composition of the ruthenium thin film through twice atomic deposition treatment, making the process more flexible and enabling customization of thin film properties according to specific application requirements.

[0149] 5. Potential reduction and improvement of cost and efficiency: The method uses a new type of precursor source and an optimized atomic deposition treatment process, which can effectively reduce the consumption of raw materials and production costs, and also improve the efficiency and yield of the final ruthenium thin film deposition.

[0150] In summary, the method for depositing and growing a ruthenium film on a glass substrate surface provided by the embodiments of the present application enables the successful deposition of a ruthenium film on a glass substrate, and exhibits obvious advantages in performance improvement, cost control, and environmental friendliness, etc. compared to traditional physical vapor deposition and chemical vapor deposition techniques, thereby improving the application potential of the ruthenium film on the glass substrate.

[0151] The above description is merely that of the embodiments of the present application, to enable those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined in the present application can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein but will be accorded the widest scope consistent with the principles and novel features described herein.

Claims

1.A method for depositing a ruthenium film on a surface of a glass substrate, the method comprising: pre-treating a glass substrate to obtain a pre-treated substrate; performing a first atomic layer deposition (ALD) process on the pre-treated substrate using a tricarbonylruthenium source in an inert atmosphere to obtain a tricarbonyl-containing rough ruthenium film substrate; performing a second ALD process on the tricarbonyl-containing rough ruthenium film substrate using an oxygen source to cause a redox reaction of the tricarbonyl in the rough ruthenium film substrate and remove the rough ruthenium film substrate to obtain a glass substrate containing a ruthenium film; the first ALD process comprises a first heating section and a tricarbonylruthenium source pulse section, the end point temperature of the first heating section is 150-200℃, and the pulse time of the tricarbonylruthenium source pulse section is 0.1-5.0s; the first ALD process further comprises a first carrier gas purge section, the time of the first carrier gas purge section is 0.1-5s, the temperature of the first carrier gas purge section is 95-105℃, and the carrier gas flow rate of the first carrier gas purge section is 10-150sccm; the second ALD process comprises a second heating section and an oxygen source pulse section, the end point temperature of the second heating section is 150-200℃, and the pulse time of the oxygen source pulse section is 0.1-1.0s; the second ALD process further comprises a second carrier gas purge section, the time of the second carrier gas purge section is 0.01-0.05s, the temperature of the second carrier gas purge section is 95-105℃, and the carrier gas flow rate of the second carrier gas purge section is 10-150sccm. 2.The method of claim 1, wherein the temperature compensation value of the first ALD process and the second ALD process is 0.05-0.40torr. 3.The method of claim 1, wherein the temperature of the tricarbonylruthenium source is 40-50℃; and / or the temperature of the oxygen source is 15-30℃. 4.The method of claim 1, wherein the species of the tricarbonylruthenium source comprises at least one of (η4-2, 3-dimethylbut-1, 3-diene) tricarbonylruthenium, (η4-but-1, 3-diene) tricarbonylruthenium, (1, 3-cyclohexadienyl) tricarbonylruthenium, (η4-2-methylbut-1, 3-diene) tricarbonylruthenium, and dodecacarbonyltriruthenium; and / or the species of the oxygen source comprises oxygen and / or water. 5.The method of claim 1, wherein the pre-treating a glass substrate to obtain a pre-treated substrate comprises the steps of: mixing anhydrous ethanol and part of deionized water to obtain a mixed solution; immersing a glass substrate in the mixed solution and performing a first ultrasonic treatment to obtain a first cleaned substrate; immersing the first cleaned substrate in the remaining deionized water and performing a second ultrasonic treatment to obtain a second cleaned substrate; drying the second cleaned substrate using an inert gas to obtain a pre-treated substrate; and wherein the time of the first ultrasonic treatment is ≥30min, and the time of the second ultrasonic treatment is ≥15min. ​ ​ 6. The method according to claim 1 or 5, the glass substrate comprising a BF33 type glass substrate.

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