Method for depositing and growing ruthenium film on surface of glass substrate

Abstract

The invention relates to the technical field of film materials, in particular to a method for depositing and growing a ruthenium film on the surface of a glass substrate. The method comprises the following steps: pre-treating a glass substrate to obtain a pre-treated substrate; carrying out primary atomic layer deposition treatment on the pre-treated substrate by using a tricarbonyl ruthenium ruthenium source under the condition of inert atmosphere to obtain a tricarbonyl-containing crude ruthenium film substrate; and carrying out secondary atomic layer deposition treatment on the crude ruthenium film substrate by using an oxygen source, so that the tricarbonyl group of the crude ruthenium film substrate is subjected to oxidation-reduction reaction, and removing the crude ruthenium film substrate to obtain the glass substrate containing the ruthenium film. According to the method, the target of depositing and growing the high-quality ruthenium film on the surface of the glass substrate is successfully achieved through ingenious combination of two times of atomic layer deposition treatment and oxidation-reduction reaction. According to the method, the purity and the uniformity of the ruthenium film are improved, the heterogeneity of the ruthenium film is controlled to be 0.35% or below, and the binding force and the stability of the ruthenium film and the glass substrate are remarkably enhanced.

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 surface. Background Art

[0002] In the manufacturing process of modern electronic and optoelectronic devices, metal films are widely used due to their unique electrical, thermal and optical properties. Ruthenium (Ru) film has become the preferred material for integrated circuit interconnection technology due to its high conductivity and good thermal stability. At present, most of the microelectronics and optoelectronics fields use glass as a substrate, and then deposit a layer of ruthenium film on the surface of the glass substrate, and then prepare devices related to modern electronics and optoelectronics based on the formed ruthenium film.

[0003] Currently, the technologies for depositing ruthenium films on glass substrates include physical vapor deposition (PVD) or chemical vapor deposition (CVD) technologies, but these deposition technologies have some limitations when depositing ruthenium films: for example, it is difficult to accurately control the thickness and uniformity of the ruthenium film growth, resulting in poor quality of the ruthenium film. Summary of the invention

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

[0005] In a first aspect, an embodiment of the present application provides a method for depositing and growing a ruthenium thin film on a glass substrate, the method comprising:

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

[0007] Using a ruthenium tricarbonyl source, the pretreated substrate is subjected to a first atomic layer deposition treatment under an inert atmosphere to obtain a rough ruthenium thin film substrate containing tricarbonyl;

[0008] The crude ruthenium film substrate containing tricarbonyl groups is subjected to a second atomic layer deposition treatment using an oxygen source, so that the tricarbonyl groups of the crude ruthenium film substrate undergo an oxidation-reduction reaction, and the crude ruthenium film substrate is removed to obtain a glass substrate containing a ruthenium film.

[0009] Optionally, the first atomic layer deposition process includes a first heating section and a ruthenium tricarbonyl type ruthenium source pulse section, the terminal temperature of the first heating section is 150°C to 200°C, and the pulse time of the ruthenium tricarbonyl type ruthenium source pulse section is 0.1s to 5.0s.

[0010] Optionally, the first atomic layer deposition process also includes a first carrier gas purge section, the duration of the first carrier gas purge section is 0.1s to 5s, the temperature of the first carrier gas purge section is 95°C to 105°C, and the carrier gas flow rate of the first carrier gas purge section is 10sccm to 150sccm.

[0011] Optionally, the second atomic layer deposition process includes a second heating section and an oxygen source pulse section, the end temperature of the second heating section is 150° C. to 200° C., and the pulse time of the oxygen source pulse section is 0.1 s to 1.0 s.

[0012] Optionally, the second atomic layer deposition process also includes a second carrier gas purge section, the time of the second carrier gas purge section is 0.01s to 0.05s, the temperature of the second carrier gas purge section is 95°C to 105°C, and the carrier gas flow rate of the second carrier purge section is 10sccm to 150sccm.

[0013] Optionally, the temperature compensation values ​​of the first atomic layer deposition process and the second atomic layer deposition process are 0.05 torr to 0.40 torr.

[0014] Optionally, the temperature of the ruthenium tricarbonyl source is 40° C. to 50° C.; and / or

[0015] The temperature of the oxygen source is 15°C to 30°C.

[0016] Optionally, the type of the tricarbonyl ruthenium source includes at least one of the following: (η4-2,3-dimethylbuta-1,3-diene)tricarbonyl ruthenium, (η4-buta-1,3-diene)tricarbonyl ruthenium, (1,3-cyclohexadienyl)tricarbonyl ruthenium, (η4-2-methylbuta-1,3-diene)tricarbonyl ruthenium and dodecacarbonyl triruthenium; and / or

[0017] The types of the oxygen source include oxygen gas and / or water.

[0018] Optionally, the pre-treating the glass substrate to obtain a pre-treated substrate comprises the steps of:

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

[0020] Using the mixed solution to soak a glass substrate, and performing a first ultrasound to obtain a first cleaned substrate;

[0021] Using the remaining deionized water to soak the first cleaned substrate, 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] Wherein, the time of the first ultrasound is ≥30 min, and the time of the second ultrasound is ≥15 min.

[0024] Optionally, the glass substrate includes a BF33 glass substrate.

[0025] The above technical solution provided by the embodiment of the present application has the following advantages compared with the prior art:

[0026] The embodiment of the present application provides a method for depositing and growing a ruthenium film on the surface of a glass substrate. The method first pre-treats the glass substrate to remove surface contaminants on the glass substrate, and then uniformly deposits ruthenium atoms of a tricarbonyl ruthenium source on the surface of the glass substrate in the form of a layered structure through a first atomic layer deposition process to preliminarily form a rough ruthenium film substrate containing tricarbonyl groups with uniform thickness, and then, through a second atomic layer deposition process, an oxygen source is used as an oxidant to promote the tricarbonyl groups of the rough ruthenium film substrate to be oxidized into a carbon-containing gas, so that the tricarbonyl groups are removed from the ruthenium film substrate, and at the same time, the rough ruthenium film is uniformly grown to form. Ruthenium film, so that a pure ruthenium film is deposited on the surface of the glass substrate; in addition, the introduction of an oxygen source can also increase the nucleation density of the ruthenium film, adjust and optimize the growth kinetics of ruthenium ions converted into ruthenium atoms and the surface energy between the glass substrate and the ruthenium film, so that the rough ruthenium film can further grow evenly to form a ruthenium film, and further improve the uniformity of the distribution of ruthenium atoms on the surface of the glass substrate, and the uniformly distributed ruthenium film can improve the quality of the ruthenium film deposited on the surface of the glass substrate; therefore, this method can effectively improve the quality of the ruthenium film deposited on the surface of the glass substrate through two atomic layer deposition processes and redox reactions. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0029] Figure 1 A schematic flow chart of a method for depositing and growing a ruthenium thin film on a glass substrate is provided for an embodiment of the present application;

[0030] Figure 2 A detailed schematic diagram of a method for depositing and growing a ruthenium thin film on a glass substrate is provided for an embodiment of the present application;

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

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

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

[0034] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0035] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be understood as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical 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, which applies regardless of the range; in addition, whenever a numerical range is indicated in this document, it is meant to include any cited number (fractional or integer) within the indicated range.

[0036] In this document, the terms including "including" and "including" mean "including but not limited to". Relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. "And / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone; where A and B can be singular or plural. "At least one" means one or more, and "plurality" means two or more; "at least one", "at least one of the following" or similar expressions, refers to any combination of these items, including any combination of single or plural items; for example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple. "Parts" such as parts by weight and parts by mass indicate the proportional relationship between the components. In the proportional relationship involved in this article, the parameters that need to be described by proportion should be understood as the first term of the proportional formula in the order of description, and the proportional numbers should be understood as the second term of the proportional formula. For example, if the mass ratio of substance A, substance B and substance C is 1:2:3, then substance A, substance B and substance C should correspond to the proportional numbers in the proportional formula in the order of description, that is, the mass of substance A: the mass of substance B: the mass of substance C = 1:2:3.

[0037] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this article can be purchased from the market or prepared by existing methods.

[0038] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this article can be purchased from the market or prepared by existing methods.

[0039] Figure 1 The present invention provides a schematic flow chart of a method for depositing and growing a ruthenium thin film on a glass substrate according to an embodiment of the present application;

[0040] Figure 5 The principle flow chart of a method for depositing and growing a ruthenium thin film on a glass substrate provided in an embodiment of the present application is exemplarily shown;

[0041] like Figure 1 and Figure 5 As shown, the embodiment of the present application provides a method for depositing and growing a ruthenium film on a glass substrate, the method comprising:

[0042] S1. Pretreating the glass substrate to obtain a pretreated substrate;

[0043] S2. Under inert atmosphere, the pretreated substrate is subjected to a first atomic layer deposition treatment using a ruthenium tricarbonyl source to obtain a rough ruthenium thin film substrate containing tricarbonyl;

[0044] S3. Use an oxygen source to perform a second atomic layer deposition treatment on the crude ruthenium film substrate containing tricarbonyl groups, so that the tricarbonyl groups of the crude ruthenium film substrate undergo an oxidation-reduction reaction, and remove the crude ruthenium film substrate to obtain a glass substrate containing a ruthenium film.

[0045] It should be noted that after pretreatment, the impurities on the surface of the glass substrate are removed, which can increase the binding sites between 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 embodiment of the present application provides a method for depositing and growing a ruthenium film on a glass substrate surface. The method is not only rigorous but also efficient. The specific steps and principles are as follows:

[0047] (1) First, the glass substrate is strictly pretreated. This step is crucial, and its purpose is to completely remove various pollutants that may exist on the surface of the glass substrate, such as dust, grease, organic residues, etc., so as to provide a clean, pollution-free surface environment for the subsequent deposition process. Pretreatment usually includes cleaning, drying and necessary surface activation treatment to ensure the best condition of the glass substrate.

[0048] (2) Next, the first atomic layer deposition process is carried out. In this stage, a ruthenium tricarbonyl ruthenium 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 ruthenium tricarbonyl are uniformly deposited on the surface of the pretreated glass substrate in the form of a layered structure. This process initially forms a coarse ruthenium film substrate with uniform thickness and containing tricarbonyl groups. Although this coarse ruthenium film has a preliminary coverage of ruthenium, its purity and structure still need to be further optimized due to the presence of tricarbonyl groups.

[0049] (3) Then, the second atomic layer deposition process is started. In this stage, an oxygen source is introduced as an oxidant. The introduction of the oxygen source has multiple functions: on the one hand, it can promote the oxidation of tricarbonyl groups in the rough ruthenium film substrate into carbon-containing gases, which are then discharged from the deposition system, thereby achieving the effective removal of tricarbonyl groups 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, so that the rough ruthenium film gradually becomes uniform and dense during the oxidation process, and finally forms a high-quality ruthenium film.

[0050] It is worth noting that the introduction of the oxygen source is not only to remove the tricarbonyl group, it also has a positive impact on the growth of the ruthenium film in many aspects. First, the oxygen source can increase the nucleation density of the ruthenium film, making the distribution of ruthenium atoms on the surface of the glass substrate more dense and uniform. Secondly, the oxygen source can adjust and optimize the growth kinetics of ruthenium ions converted 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 film, further enhancing the bonding force and stability between the ruthenium film and the glass substrate.

[0051] In summary, the embodiment of the present application successfully achieves the goal of depositing and growing high-quality ruthenium thin films on the surface of glass substrates through the clever 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 strength and stability with the glass substrate, providing strong support for applications in related fields.

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

[0053] In these embodiments, the first atomic layer deposition process may include a first heating section and a ruthenium tricarbonyl-based ruthenium source pulse section, and the terminal temperature of the first heating section may be 150°C to 200°C, and the pulse time of the ruthenium tricarbonyl-based ruthenium source pulse section may be 0.1s to 5.0s, thereby causing the ruthenium atoms of the ruthenium tricarbonyl-based ruthenium source to be uniformly deposited on the surface of the glass substrate in the form of a layered structure during the first atomic layer deposition process to preliminarily form a coarse ruthenium film with uniform thickness.

[0054] The endpoint temperature of the first heating stage may be 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

[0055] The pulse time of the tricarbonylruthenium 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 section, the time of the first carrier gas purge section is 0.1s to 5s, the temperature of the first carrier gas purge section is 95°C to 105°C, and the carrier gas flow rate of the first carrier gas purge section is 10sccm to 150sccm;

[0057] In these embodiments, the first atomic layer deposition treatment may further include a first carrier gas purging section, and the time of the first carrier gas purging section may be 0.1s to 5s, and the temperature of the first carrier gas purging section may be 95°C to 105°C, and the carrier gas flow rate of the first carrier gas purging section may be 10sccm to 150sccm, so that the ruthenium atoms remaining from the first atomic layer deposition treatment and the unreacted tricarbonyl ruthenium ruthenium source are fully blown out of the atomic layer deposition treatment equipment through the first carrier gas purging section, so as to facilitate the subsequent second atomic layer deposition treatment and obtain a ruthenium film with uniform thickness distribution.

[0058] The time of the first carrier gas purge section can be 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 temperature of the first carrier gas purge section can be 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C or 105°C.

[0060] The carrier gas flow rate of the first carrier gas purge section may be 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.

[0061] In some optional embodiments, the second atomic layer deposition process includes a second heating section and an oxygen source pulse section, the end temperature of the second heating section is 150° C. to 200° C., and the pulse time of the oxygen source pulse section is 0.01 s to 1.0 s;

[0062] In these embodiments, the second atomic layer deposition process may include a second heating section and an oxygen source pulse section, and the terminal temperature of the second heating section may be 150°C to 200°C, and the pulse time of the oxygen source pulse section may be 0.01s to 10.0s, so that the tricarbonyl group of the rough ruthenium film is oxidized into a carbon-containing gas (carbon monoxide or carbon dioxide) under the oxidation conditions of the oxygen source, so that the rough ruthenium film grows uniformly to form a high-purity ruthenium film, and the ruthenium film is uniformly deposited on the surface of the glass substrate.

[0063] The endpoint temperature of the second heating stage may be 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

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

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

[0066] In these embodiments, the second atomic layer deposition treatment may further include a second carrier gas purging section, and the time of the second carrier gas purging section may be 0.01s to 0.05s, and the temperature of the second carrier gas purging section may be 95°C to 105°C, and the carrier gas flow rate of the second carrier purging section may be 10sccm to 150sccm, so that the oxygen source remaining from the second atomic layer deposition treatment is fully blown out of the atomic layer deposition treatment equipment through the second carrier gas purging section, so as to facilitate the atomic layer deposition treatment in the subsequent cycle stage and obtain a ruthenium film with uniform thickness distribution.

[0067] The duration of the second carrier gas purge section can be 0.01 s, 0.02 s, 0.03 s, 0.04 s or 0.05 s.

[0068] The temperature of the second carrier gas purge section can be 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 carrier gas flow rate of the second carrier purge section may be 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 optional 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 0.05torr to 0.40torr, which enables the first atomic layer deposition process and the second atomic layer deposition process to be fully performed, thereby forming a ruthenium film with sufficient thickness and uniform distribution on the glass substrate.

[0072] The temperature compensation values ​​of the first atomic layer deposition process and the second atomic layer deposition process may 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 optional embodiments, the temperature of the ruthenium tricarbonyl source is 40° C. to 50° C.; and / or

[0074] The temperature of the oxygen source is 15°C to 30°C;

[0075] In these embodiments, the temperature of the tricarbonyl ruthenium source can be 40°C to 50°C, which enables the temperature of the tricarbonyl ruthenium source in the first atomic layer deposition treatment to be within a suitable range, so as to facilitate the first atomic layer deposition treatment to be fully carried out and obtain a coarse ruthenium film with sufficient thickness and uniform distribution; in addition, the temperature of the oxygen source can be 15°C to 30°C, which enables the temperature of the oxygen source in the second atomic layer deposition treatment to be within a suitable range, so as to facilitate the second atomic layer deposition treatment to be fully carried out, thereby obtaining a ruthenium film with sufficient thickness and uniform distribution.

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

[0077] The temperature of the oxygen source can be 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 optional embodiments, the type of the tricarbonyl ruthenium source includes at least one of the following: (η4-2,3-dimethylbuta-1,3-diene)tricarbonyl ruthenium, (η4-buta-1,3-diene)tricarbonyl ruthenium, (1,3-cyclohexadienyl)tricarbonyl ruthenium, (η4-2-methylbuta-1,3-diene)tricarbonyl ruthenium and dodecacarbonyl triruthenium; and / or

[0079] The types of the oxygen source include oxygen and / or water;

[0080] In these embodiments, the type of ruthenium tricarbonyl source may include: at least one of (η4-2,3-dimethylbuta-1,3-diene)tricarbonylruthenium, (η4-buta-1,3-diene)tricarbonylruthenium, (1,3-cyclohexadienyl)tricarbonylruthenium, (η4-2-methylbuta-1,3-diene)tricarbonylruthenium and dodecacarbonyltriruthenium, which can cover most of the ruthenium tricarbonyl sources for atomic layer deposition processing to form a coarse ruthenium film with sufficient thickness and uniform dispersion during the first atomic layer deposition process; in addition, the type of oxygen source includes oxygen and / or water, which can cover most of the oxygen sources for atomic layer deposition processing. These oxygen sources can act as oxidants to oxidize the tricarbonyl groups of the rough ruthenium film into carbon-containing gases, 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 ruthenium ions converted 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 The detailed process diagram of a method for depositing and growing a ruthenium thin film on a glass substrate provided by an embodiment of the present application is exemplarily shown;

[0082] In some optional embodiments, such as Figure 2 As shown, the glass substrate is pretreated to obtain a pretreated substrate, comprising the steps of:

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

[0084] S102. Soaking the glass substrate in the mixed solution and performing a first ultrasound to obtain a first cleaned substrate;

[0085] S103. Soaking the first cleaning substrate with the remaining deionized water and performing a second ultrasonic treatment to obtain a second cleaning substrate;

[0086] S104. Drying the second cleaned substrate using an inert gas to obtain a pretreated substrate;

[0087] Wherein, the time of the first ultrasound is ≥30 min, and the time of the second ultrasound is ≥15 min;

[0088] In these embodiments, anhydrous ethanol and deionized water are mixed to form a cleaning solution, and then a first ultrasonic method is used to effectively remove organic impurities and inorganic impurities from the glass substrate, thereby obtaining a pure first cleaned substrate; in addition, deionized water is used as the cleaning solution and a second ultrasonic method is used to further remove the mixed liquid components and other impurities, thereby obtaining a pure second cleaned substrate.

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

[0090] It should be noted that the inert gas may be nitrogen or a single gas of a Group 0 element; the drying method may be blow drying.

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

[0092] In these embodiments, the glass substrate may include a BF33 glass substrate, which is a high borosilicate glass produced by Schott. As a glass substrate, the BF33 glass substrate has a smoother surface and more binding sites to facilitate the deposition of ruthenium atoms of a tricarbonyl ruthenium source on the surface of the glass substrate and form a rough ruthenium film.

[0093] The present application is further described below in conjunction with specific examples. The experimental methods in the following examples where specific conditions are not specified are usually measured in accordance with national standards / industry standards; if there are no corresponding national standards / industry standards, they are measured in accordance with common international standards, conventional conditions or conditions recommended by the manufacturer.

[0094] Example 1

[0095] like Figure 2 and Figure 5 As shown, a method for depositing and growing a ruthenium film on a glass substrate surface comprises:

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

[0097] S102. Using the mixed solution to completely immerse the BF33 glass substrate of Schott, and performing a first ultrasonic treatment to remove impurities and contaminants on the surface of the glass substrate to obtain a first cleaned substrate;

[0098] S103. Using the remaining deionized water to completely immerse the first cleaning substrate, and performing a second ultrasound to obtain a second cleaning substrate;

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

[0100] The first ultrasound was performed for 30 minutes and the second ultrasound was performed for 15 minutes.

[0101] Set the temperature of the heating section (Heater) of the atomic layer deposition reaction chamber to 200°C, and then keep the TOP (Temperature of Precursor) of the atomic layer deposition reaction chamber consistent with the temperature of the Heater;

[0102] S2. introducing a ruthenium tricarbonyl source into an atomic layer deposition reaction chamber, and performing a first atomic layer deposition treatment on the pretreated substrate using the ruthenium tricarbonyl source under an inert 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 the condition of an inert gas atmosphere, so that the rough ruthenium film undergoes a reduction reaction to obtain a glass substrate containing the ruthenium film.

[0104] The above-mentioned first atomic layer deposition process and the second atomic layer deposition process are repeated according to the required thickness of the ruthenium film. Each cycle will deposit one or more layers of metal atoms on the glass substrate, so by accurately controlling the number of cycles, the thickness of the ruthenium film can be accurately controlled. The total number of cycles of the first atomic layer deposition process and the second atomic layer deposition process is 100 times, and the growth rate of the ruthenium film in each cycle is 2.128 angstroms / cycle.

[0105] The first atomic layer deposition process includes a first heating section and a ruthenium tricarbonyl type ruthenium source pulse section. The terminal temperature of the first heating section is 200° C., and the pulse time of the ruthenium tricarbonyl type ruthenium source pulse section is 5.0 s.

[0106] The first atomic layer deposition process also includes a first carrier gas purge section. The duration of the first carrier gas purge section is 2 seconds. The temperature of the first carrier gas purge section is 100° C. and the carrier gas flow rate of the first carrier gas purge section is 15 sccm.

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

[0108] The second atomic layer deposition process also includes a second carrier gas purge section, the duration of the second carrier gas purge section is 0.02 s, the temperature of the second carrier gas purge section is 100° C., and the carrier gas flow rate of the second carrier gas purge section is 15 sccm.

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

[0110] The temperature of the ruthenium tricarbonyl source is 48°C;

[0111] The temperature of the oxygen source was 25°C.

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

[0113] The type of oxygen source is water.

[0114] Example 2

[0115] Based on the contents disclosed in Example 1, the following modifications are further made:

[0116] The terminal temperature of the first heating section is 150° C., and the pulse time of the tricarbonyl ruthenium source pulse section is 0.1 s.

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

[0118] The end temperature of the second heating section was 150°C, and the pulse time of the oxygen source pulse section was 1.0 s.

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

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

[0121] The temperature of the ruthenium tricarbonyl source is 40°C;

[0122] The temperature of the oxygen source was 20°C.

[0123] Example 3

[0124] Based on the contents disclosed in Example 1, the following modifications are further made:

[0125] The terminal temperature of the first heating section is 175° C., and the pulse time of the tricarbonyl ruthenium source pulse section is 5.0 s.

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

[0127] The end temperature of the second heating section was 175°C, and the pulse time of the oxygen source pulse section was 10.0 s.

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

[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 tricarbonyl source is 50°C;

[0131] The temperature of the oxygen source was 30°C.

[0132] Comparative Example 1

[0133] Based on the contents disclosed in Example 1, the following modifications are further made:

[0134] The ruthenium film of the same thickness was formed using conventional physical vapor deposition method.

[0135] Comparative Example 2

[0136] Based on the contents disclosed in Example 1, the following modifications are further made:

[0137] The ruthenium film of the same thickness was formed using conventional chemical vapor deposition method.

[0138] Related experiments and effect data:

[0139] Take the glass substrate sample containing the ruthenium film obtained in Example 1, select three sampling points respectively, and statistically analyze the distribution of the ruthenium film thickness. The characteristics of the surface and cross section of the ruthenium film in a certain area are as follows: Figure 3 As shown in the figure, and the EDS test results are as follows Figure 4 As shown, the thickness of the ruthenium film at the two sampling points is 21.35nm and 21.21nm respectively, and the calculated non-uniformity is 0.329%. According to this process, the glass substrate samples containing ruthenium film in each embodiment and comparative example are sampled and the non-uniformity is calculated, and the results are shown in Table 1. The calculation formula is: non-uniformity coefficient w = (maximum value of ruthenium film thickness - minimum value of ruthenium film thickness) / (maximum value of ruthenium film thickness + minimum value of ruthenium film thickness).

[0140] Table 1 Non-uniformity results of glass substrate samples containing ruthenium films in various embodiments and comparative examples

[0141]

[0142]

[0143] As can be seen from Table 1, the embodiment of the present application provides a method for depositing and growing a ruthenium film on a glass substrate surface. The method successfully achieves the goal of depositing and growing a high-quality ruthenium film on the glass substrate surface through a clever combination of two atomic layer deposition processes and redox reactions. This method not only improves the purity and uniformity of the ruthenium film, but also significantly enhances its bonding strength and stability with the glass substrate, providing strong support for applications in related fields, so that the non-uniformity of the ruthenium film is controlled below 0.35%, and provides new technical approaches and solutions for the development of related fields.

[0144] In addition, the embodiment of the present application provides a method for depositing and growing a ruthenium film on a glass substrate, which also has the following characteristics:

[0145] 1. Innovative application of substrate materials: Traditional atomic deposition processing technology is mainly used for semiconductor materials such as silicon wafers, while the method of this application successfully deposits ruthenium thin films on glass substrates. This innovation broadens the application field of atomic deposition processing technology and provides new possibilities for the application of glass materials in the fields of electronics and optoelectronics.

[0146] 2. Use of new precursor sources: This method uses a new precursor source for the deposition of ruthenium thin films, which may bring higher reactivity and selectivity, improve the quality and performance of the film, while reducing side reactions and waste generation, and improving the environmental protection and economy of the process.

[0147] 3. Potential improvement in film performance: This method deposits ruthenium thin films on glass substrates through atomic deposition. Due to the high uniformity and precise thickness control of the atomic deposition process, the ruthenium thin films have excellent electrical conductivity, thermal stability and catalytic activity, which are crucial to improving the performance of related devices.

[0148] 4. Enhanced process flexibility and controllability: This method can precisely control the thickness and composition of the ruthenium film through two atomic deposition processes, making the process more flexible and able to customize the film properties according to specific application requirements.

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

[0150] In summary, the embodiment of the present application provides a method for depositing and growing a ruthenium thin film on the surface of a glass substrate. This method enables the ruthenium thin film to be successfully deposited on a glass substrate. Compared with traditional physical vapor deposition technology and chemical vapor deposition technology, this method exhibits obvious advantages in performance improvement, cost control, and environmental friendliness, thereby increasing the application potential of ruthenium thin films on glass substrates.

[0151] The above description is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. It will be apparent to those skilled in the art that various modifications to these embodiments are possible, and the general 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 in the present application, but will conform to the widest range consistent with the principles and novel features applied for by the present application.

Claims

1. A method for depositing and growing a ruthenium thin film on a glass substrate, the method comprising: Pre-treating the glass substrate to obtain a pre-treated substrate; Using a ruthenium tricarbonyl source, the pretreated substrate is subjected to a first atomic layer deposition treatment under an inert atmosphere to obtain a rough ruthenium thin film substrate containing tricarbonyl; The crude ruthenium film substrate containing tricarbonyl groups is subjected to a second atomic layer deposition treatment using an oxygen source, so that the tricarbonyl groups of the crude ruthenium film substrate undergo an oxidation-reduction reaction, and the crude ruthenium film substrate is removed to obtain a glass substrate containing a ruthenium film.

2. According to the method described in claim 1, the first atomic layer deposition process includes a first heating section and a ruthenium tricarbonyl ruthenium source pulse section, the terminal temperature of the first heating section is 150°C to 200°C, and the pulse time of the ruthenium tricarbonyl ruthenium source pulse section is 0.1s to 5.0s.

3. According to the method described in claim 2, the first atomic layer deposition process also includes a first carrier gas purge section, the time of the first carrier gas purge section is 0.1s to 5s, the temperature of the first carrier gas purge section is 95°C to 105°C, and the carrier gas flow rate of the first carrier gas purge section is 10sccm to 150sccm.

4. According to the method of claim 1, the second atomic layer deposition process includes a second heating section and an oxygen source pulse section, the terminal temperature of the second heating section is 150°C to 200°C, and the pulse time of the oxygen source pulse section is 0.1s to 1.0s.

5. According to the method described in claim 4, the second atomic layer deposition process also includes a second carrier gas purge section, the time of the second carrier gas purge section is 0.01s to 0.05s, the temperature of the second carrier gas purge section is 95°C to 105°C, and the carrier gas flow rate of the second carrier purge section is 10sccm to 150sccm. 6 . The method according to claim 1 , wherein the temperature compensation values ​​of the first atomic layer deposition process and the second atomic layer deposition process are 0.05 torr to 0.40 torr.

7. The method according to claim 1, wherein the temperature of the ruthenium tricarbonyl source is 40°C to 50°C; and / or The temperature of the oxygen source is 15°C to 30°C.

8. The method according to claim 1, wherein the type of the tricarbonyl ruthenium source comprises at least one of (η4-2,3-dimethylbuta-1,3-diene)tricarbonyl ruthenium, (η4-buta-1,3-diene)tricarbonyl ruthenium, (1,3-cyclohexadienyl)tricarbonyl ruthenium, (η4-2-methylbuta-1,3-diene)tricarbonyl ruthenium and dodecacarbonyl triruthenium; and / or The types of the oxygen source include oxygen gas and / or water.

9. The method according to claim 1, wherein the pre-treating the glass substrate to obtain the pre-treated substrate comprises the steps of: Mixing anhydrous ethanol and part of deionized water to obtain a mixed solution; Using the mixed solution to soak a glass substrate, and performing a first ultrasound to obtain a first cleaned substrate; Using the remaining deionized water to soak the first cleaned substrate, and performing a second ultrasonic treatment to obtain a second cleaned substrate; drying the second cleaned substrate using an inert gas to obtain a pretreated substrate; Wherein, the time of the first ultrasound is ≥30 min, and the time of the second ultrasound is ≥15 min.

10. The method according to claim 1 or 9, wherein the glass substrate comprises a BF33 type glass substrate.

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