Method for depositing and growing copper 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 copper 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 pretreated substrate by using a copper source under the condition of inert atmosphere to obtain a crude substrate containing a crude copper film; and carrying out secondary atomic layer deposition treatment on the crude substrate containing the crude copper film by using a zinc source under the condition of inert gas atmosphere, so that the crude copper film is subjected to reduction reaction, and the glass substrate containing the copper film is obtained. According to the method, high-uniformity growth of the copper thin film on the glass substrate is realized through fine technological process design and an innovative zinc source introduction strategy by utilizing a mode of twice atomic layer deposition treatment, so that the heterogeneity of the copper thin film is controlled below 2.5%, and a new technical approach and a new solution are provided for development of related fields.

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 copper thin film on a glass substrate surface. Background Art

[0002] In the field of microelectronics and optoelectronics, metal films are widely used due to their unique electrical, thermal and optical properties. Copper (Cu) film has become the preferred material for integrated circuit interconnection technology due to its high conductivity and good thermal stability. At present, the microelectronics and optoelectronics fields mostly use glass as a substrate, and then deposit a layer of copper film on the surface of the glass substrate, and then prepare devices related to the microelectronics and optoelectronics fields based on the formed copper film.

[0003] Currently, the technologies for depositing copper films on glass substrates include physical vapor deposition (PVD) or chemical vapor deposition (CVD) technologies, but these deposition technologies have some limitations when depositing copper films: for example, it is difficult to accurately control the thickness and uniformity of the copper film growth. In addition, these deposition technologies will also produce defects on the surface of the glass substrate, further deteriorating the uniformity of the copper film. Summary of the invention

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

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

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

[0007] Using a copper source to perform a first atomic layer deposition treatment on the pretreated substrate under an inert atmosphere to obtain a rough substrate containing a rough copper film;

[0008] The rough substrate containing the rough copper film is subjected to a second atomic layer deposition treatment using a zinc source under an inert gas atmosphere, so that the rough copper film undergoes a reduction reaction to obtain a glass substrate containing a copper film.

[0009] Optionally, the first atomic layer deposition process includes a first heating section and a copper source pulse section, the terminal temperature of the first heating section is 150° C. to 200° C., and the pulse time of the copper source pulse section is 0.1 s to 10.0 s.

[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 20s, the temperature of the first carrier gas purge section is 75°C to 85°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 a zinc source pulse section, the end temperature of the second heating section is 150° C. to 200° C., and the pulse time of the zinc source pulse section is 0.01 s to 10.0 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 0.1s to 20s, 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 copper source is 60° C. to 100° C.; and / or

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

[0016] Optionally, the type of the copper source includes at least one of the following: copper sulfide, basic copper carbonate and bis(hexafluoroacetylacetonate)copper; and / or

[0017] The zinc source includes at least one of the following: zinc oxide, zinc chloride and diethyl zinc.

[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 copper 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 uses a first atomic layer deposition process to uniformly deposit copper atoms of a copper source on the surface of the glass substrate in the form of a layered structure to preliminarily form a rough copper film with uniform thickness. Then, a second atomic layer deposition process is performed, using a zinc source as a reducing agent to promote the reduction of copper ions in the rough copper film into copper atoms, so that the rough copper film uniformly grows to form a copper film, and the copper film is deposited on the surface of the glass substrate; in addition, the introduction of the zinc source can also increase the nucleation density of the copper film, adjust and optimize the growth kinetics of copper ions converted into copper atoms and the surface energy between the glass substrate and the copper film, so that the rough copper film further uniformly grows to form a copper film, and further improves the uniformity of the distribution of copper atoms on the surface of the glass substrate; therefore, the method can effectively improve the uniformity of the growth of the copper film through two atomic layer deposition processes and a reduction reaction. 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 copper 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 copper thin film on a glass substrate is provided for an embodiment of the present application;

[0031] Figure 3 A schematic diagram of a sample of a glass substrate containing a copper thin film provided in Example 1 of the present application;

[0032] Figure 4 This is a graph showing the surface characteristics of a glass substrate containing a copper film provided in Example 1 of the present application; Figure 4 a is the scanning electron microscope result of the copper film surface at a scale of 500nm. Figure 4b is the scanning electron microscope result of the copper film surface at a scale of 100 nm. Figure 4 c is the scanning electron microscope result of the copper film cross section at a scale of 100 nm. Figure 4 d is the SEM result of the cross section of the copper film at three sampling points selected at a scale of 100 nm;

[0033] Figure 5 This is an X-ray photoelectron spectroscopy result diagram of a glass substrate containing a copper thin film provided in Example 1 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] Figure 1 The present invention provides a schematic flow chart of a method for depositing and growing a copper thin film on a glass substrate provided by an embodiment of the present invention;

[0039] like Figure 1 As shown, the embodiment of the present application provides a method for depositing and growing a copper thin film on a glass substrate, the method comprising:

[0040] S1. Pre-treating the BF33 glass substrate to obtain a pre-treated substrate;

[0041] S2. Under inert atmosphere, the pretreated substrate is subjected to a first atomic layer deposition process using a copper source to obtain a rough substrate containing a rough copper film;

[0042] S3. Under the condition of an inert gas atmosphere, the rough substrate containing the rough copper film is subjected to a second atomic layer deposition treatment using a zinc source, so that the rough copper film undergoes a reduction reaction to obtain a glass substrate containing a copper film.

[0043] It should be noted that the impurities on the surface of the glass substrate after pretreatment can be removed, which can increase the binding sites between copper atoms and the glass substrate in the subsequent first atomic layer deposition treatment stage, so that a rough copper film can be initially grown on the surface of the glass substrate;

[0044] It should be noted that the embodiment of the present application provides a method for depositing and growing a copper thin film on a glass substrate. The method achieves high uniformity growth of the copper thin film on the glass substrate through a sophisticated process design. The following are the detailed steps of the method and its advantages:

[0045] First, the glass substrate is pretreated. This step is crucial, as it aims to completely remove various contaminants on the surface of the glass substrate, such as grease, dust and impurities, to lay a good foundation for the subsequent atomic layer deposition process. Pretreatment can ensure that copper atoms can be more evenly attached to the glass substrate during the deposition process, avoiding uneven deposition caused by contaminants.

[0046] Next, the first atomic layer deposition process is carried out. In this step, a specific copper source is selected, and the copper atoms are uniformly deposited on the surface of the pre-treated glass substrate in the form of a layered structure through atomic layer deposition technology. In this process, the copper atoms will stack layer by layer to form a preliminary rough copper film with uniform thickness. The self-limiting characteristics of atomic layer deposition technology ensure that the thickness of the copper atomic layer deposited each time is precisely controllable, thus laying the foundation for achieving high-quality copper films.

[0047] Then, a second atomic layer deposition process is performed, and a zinc source is introduced as a reducing agent. This is the core innovation of this method. During the second atomic layer deposition process, a zinc source is cleverly introduced, which, as a reducing agent, can cause the copper ions in the rough copper film to be reduced to copper atoms. This reduction reaction not only promotes the uniform growth of the copper film, but also allows the copper film to be deposited more densely on the surface of the glass substrate. At the same time, the introduction of the zinc source also brings additional advantages: it increases the nucleation density of the copper film, adjusts the growth kinetics of the conversion of copper ions into copper atoms, and optimizes the surface energy between the glass substrate and the copper film. These effects together promote the further uniform growth of the rough copper film and form a high-quality copper film.

[0048] Finally, through the synergistic effect of two atomic layer deposition processes and reduction reaction, this method effectively improves the uniformity of copper film growth. Compared with the traditional deposition method, this method not only achieves high uniformity growth of copper film on glass substrate, but also further optimizes the growth process and performance of copper film by introducing zinc source as reducing agent. This makes the prepared copper film show excellent performance in optics, electricity and thermal aspects, providing strong support for applications in related fields.

[0049] In summary, the embodiments of the present application provide a method for growing a copper thin film by deposition on a glass substrate surface. The method achieves highly uniform growth of the copper thin film on the glass substrate through sophisticated process design and an innovative zinc source introduction strategy, thus providing a new technical approach and solution for the development of related fields.

[0050] In some optional embodiments, the first atomic layer deposition process includes a first heating section and a copper source pulse section, the end temperature of the first heating section is 150° C. to 200° C., and the pulse time of the copper source pulse section is 0.1 s to 10.0 s;

[0051] In these embodiments, the first atomic layer deposition process may include a first heating section and a copper 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 copper source pulse section may be 0.1s to 10.0s, thereby causing the copper atoms of the copper 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 rough copper film with uniform thickness.

[0052] The endpoint temperature of the first heating stage may be 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

[0053] The pulse time of the copper source pulse segment can be 0.1s, 0.2s, 0.3s, 0.4s, 0.5s, 1.0s, 2.0s, 3.0s, 4.0s, 5.0s, 6.0s, 7.0s, 8.0s, 9.0s or 10.0s.

[0054] 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 20s, the temperature of the first carrier gas purge section is 75°C to 85°C, and the carrier gas flow rate of the first carrier gas purge section is 10sccm to 150sccm;

[0055] 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 20s, and the temperature of the first carrier gas purging section may be 75°C to 85°C, and the carrier gas flow rate of the first carrier gas purging section may be 10sccm to 150sccm, so that the copper atoms remaining from the first atomic layer deposition treatment 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 copper film with uniform thickness distribution.

[0056] 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.

[0057] The temperature of the first carrier gas purge section can be 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C or 85°C.

[0058] 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.

[0059] In some optional embodiments, the second atomic layer deposition process includes a second heating section and a zinc source pulse section, the end temperature of the second heating section is 150° C. to 200° C., and the pulse time of the zinc source pulse section is 0.01 s to 10.0 s;

[0060] In these embodiments, the second atomic layer deposition process may include a second heating section and a zinc 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 zinc source pulse section may be 0.01s to 10.0s, so that the copper ions of the rough copper film are reduced to copper atoms under the reducing conditions of the zinc source, so that the rough copper film grows uniformly to form a copper film, and the copper film is uniformly deposited on the surface of the glass substrate.

[0061] The endpoint temperature of the second heating stage may be 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

[0062] The pulse time of the zinc source pulse segment can be 0.01s, 0.05s, 0.06s, 0.07s, 0.08s, 0.09s, 0.1s, 0.2s, 0.3s, 0.4s, 0.5s, 1.0s, 2.0s, 3.0s, 4.0s, 5.0s or 10.0s.

[0063] 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 0.1s to 20s, 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;

[0064] 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 0.1s to 20s, 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 zinc 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 copper film with uniform thickness distribution.

[0065] The time of the second 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 or 10.0s.

[0066] 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.

[0067] 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;

[0068] 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 copper film with sufficient thickness and uniform distribution on the glass substrate.

[0069] 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.

[0070] In some optional embodiments, the temperature of the copper source is 60° C. to 100° C.; and / or

[0071] The temperature of the zinc source is 15°C to 30°C;

[0072] In these embodiments, the temperature of the copper source can be 60°C to 100°C, which causes the temperature of the copper 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 rough copper film with sufficient thickness and uniform distribution. In addition, the temperature of the zinc source can be 15°C to 30°C, which causes the temperature of the zinc 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 copper film with sufficient thickness and uniform distribution.

[0073] The temperature of the copper source may be 60°C, 70°C, 80°C, 90°C or 100°C.

[0074] The temperature of the zinc source may 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.

[0075] In some optional embodiments, the type of copper source includes at least one of the following: copper sulfide, basic copper carbonate and bis(hexafluoroacetylacetonate)copper; and / or

[0076] The type of the zinc source includes at least one of the following: zinc oxide, zinc chloride and diethyl zinc;

[0077] In these embodiments, the types of copper sources may include: at least one of copper sulfide, basic copper carbonate and bis(hexafluoroacetylacetonate)copper, which can cover most of the copper sources for atomic layer deposition treatment, so as to form a rough copper film with sufficient thickness and uniform dispersion during the first atomic layer deposition treatment; in addition, the types of zinc sources include: at least one of zinc oxide, zinc chloride and diethyl zinc, which can cover most of the zinc sources for atomic layer deposition treatment, and these zinc sources can be used as reducing agents to reduce the copper ions of the rough copper film into copper atoms, so that the rough copper film grows uniformly to form a copper film, and the copper film is deposited on the surface of the glass substrate; in addition, these zinc sources can also increase the nucleation density of the copper film, adjust and optimize the growth kinetics of copper ions converted into copper atoms and the surface energy between the glass substrate and the copper film, so that the rough copper film further grows uniformly to form a copper film, and further improves the uniformity of the distribution of copper atoms on the surface of the glass substrate.

[0078] Figure 2 The detailed process diagram of a method for depositing and growing a copper thin film on a glass substrate provided by an embodiment of the present application is exemplarily shown;

[0079] In some optional embodiments, such as Figure 2 As shown, the glass substrate is pretreated to obtain a pretreated substrate, comprising the steps of:

[0080] S101. Mixing anhydrous ethanol and part of deionized water to obtain a mixed solution;

[0081] S102. Soaking the glass substrate in the mixed solution and performing a first ultrasound to obtain a first cleaned substrate;

[0082] S103. Soaking the first cleaning substrate with the remaining deionized water and performing a second ultrasonic treatment to obtain a second cleaning substrate;

[0083] S104. Drying the second cleaned substrate using an inert gas to obtain a pretreated substrate;

[0084] Wherein, the time of the first ultrasound is ≥30 min, and the time of the second ultrasound is ≥15 min;

[0085] 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.

[0086] 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.

[0087] 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.

[0088] In some optional embodiments, the glass substrate comprises a BF33 glass substrate;

[0089] 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 bonding sites to facilitate the deposition of copper atoms from the copper source on the surface of the glass substrate and form a rough copper film.

[0090] 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.

[0091] Example 1

[0092] like Figure 2 As shown, a method for depositing and growing a copper thin film on a glass substrate surface comprises:

[0093] S101. Mixing anhydrous ethanol and part of deionized water in a mass ratio of 1:1 to obtain a mixed solution;

[0094] 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;

[0095] S103. Using the remaining deionized water to completely immerse the first cleaning substrate, and performing a second ultrasound to obtain a second cleaning substrate;

[0096] S104. Blowing the second cleaned substrate dry using nitrogen to obtain a pretreated substrate;

[0097] The first ultrasound was performed for 30 minutes and the second ultrasound was performed for 15 minutes.

[0098] The temperature of the heating section (Heater) of the atomic layer deposition reaction chamber is set at 150°C to 200°C, and then the TOP (Temperature of Precursor) of the atomic layer deposition reaction chamber is kept consistent with the temperature of the Heater;

[0099] S2. introducing a copper source into an atomic layer deposition reaction chamber, and performing a first atomic layer deposition treatment on the pretreated substrate using the copper source under an inert atmosphere to obtain a rough substrate containing a rough copper film;

[0100] S3. Introduce a zinc source into an atomic layer deposition reaction chamber, and use the zinc source to perform a second atomic layer deposition treatment on the rough substrate containing the rough copper film under an inert gas atmosphere, so that the rough copper film undergoes a reduction reaction to obtain a glass substrate containing a copper film.

[0101] The above-mentioned first atomic layer deposition process and the second atomic layer deposition process are repeated according to the required thickness of the copper 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 copper 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 600 times, and the growth rate of the copper film in each cycle is 0.791 angstroms / cycle.

[0102] The first atomic layer deposition process includes a first heating section and a copper source pulse section. The end temperature of the first heating section is 175° C., and the pulse time of the copper source pulse section is 2.0 s.

[0103] 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 80° C. and the carrier gas flow rate of the first carrier gas purge section is 30 sccm.

[0104] The second atomic layer deposition process includes a second heating section and a zinc source pulse section. The end temperature of the second heating section is 175° C., and the pulse time of the zinc source pulse section is 0.05 s.

[0105] The second atomic layer deposition process also includes a second carrier gas purge section. The duration of the second carrier gas purge section is 20 seconds. 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 30 sccm.

[0106] The temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process is 0.10 torr.

[0107] The temperature of the copper source is 60°C;

[0108] The temperature of the zinc source was 25°C.

[0109] The type of copper source is bis(hexafluoroacetylacetonate)copper;

[0110] The type of zinc source is diethylzinc.

[0111] Example 2

[0112] Based on the contents disclosed in Example 1, the following modifications are further made:

[0113] The end temperature of the first heating section is 150° C., and the pulse time of the copper source pulse section is 0.5 s.

[0114] The time of the first carrier gas purge section is 1 s, the temperature of the first carrier gas purge section is 75° C., and the carrier gas flow rate of the first carrier gas purge section is 20 sccm.

[0115] The end temperature of the second heating section was 150°C, and the pulse time of the zinc source pulse section was 1.0 s.

[0116] The time of the second carrier gas purge section is 5 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.

[0117] The temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process is 0.05 torr.

[0118] The temperature of the copper source is 70°C;

[0119] The temperature of the zinc source was 20°C.

[0120] Example 3

[0121] Based on the contents disclosed in Example 1, the following modifications are further made:

[0122] The end temperature of the first heating section was 200° C., and the pulse time of the copper source pulse section was 5.0 s.

[0123] The time of the first carrier gas purge section is 15 s, the temperature of the first carrier gas purge section is 85° C., and the carrier gas flow rate of the first carrier gas purge section is 100 sccm.

[0124] The end temperature of the second heating section was 200°C, and the pulse time of the zinc source pulse section was 10.0 s.

[0125] The time of the second carrier gas purge section is 15 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.

[0126] The temperature compensation value of the first atomic layer deposition process and the second atomic layer deposition process is 0.40 torr.

[0127] The temperature of the copper source is 100°C;

[0128] The temperature of the zinc source was 30°C.

[0129] Comparative Example 1

[0130] Based on the contents disclosed in Example 1, the following modifications are further made:

[0131] A copper film of the same thickness is formed using conventional physical vapor deposition.

[0132] Comparative Example 2

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

[0134] A copper film of the same thickness is formed using conventional chemical vapor deposition.

[0135] Related experiments and effect data:

[0136] Take the glass substrate sample containing the copper film obtained in Example 1, such as Figure 3 As shown in Figure 2, three sampling points were selected to statistically analyze the distribution of the copper film thickness. The surface and cross-section of the copper film at a certain point are characterized as follows: Figure 4 As shown in the figure, and the results of its X-ray photoelectron spectroscopy, as shown in the figure Figure 5 As shown, the thickness of the copper film at the three sampling points is 64.2, 61.41, and 64.2, respectively, and the calculated non-uniformity is 2.2%. According to this process, the glass substrate samples containing copper films 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 copper film thickness - minimum copper film thickness) / (maximum copper film thickness + minimum copper film thickness).

[0137] Table 1 Non-uniformity results of glass substrate samples containing copper thin films in various embodiments and comparative examples

[0138]

[0139] As can be seen from Table 1, the embodiment of the present application provides a method for depositing and growing a copper thin film on a glass substrate. The method achieves highly uniform growth of a copper thin film on a glass substrate by means of a sophisticated process flow design and an innovative zinc source introduction strategy, using two atomic layer deposition treatments, so that the non-uniformity of the copper thin film is controlled below 2.5%, providing a new technical approach and solution for the development of related fields.

[0140] In addition, the embodiment of the present application provides a method for depositing and growing a copper thin film on a glass substrate, which also has the following characteristics:

[0141] 1. Innovation in precursor selection: This method uses copper bis(hexafluoroacetylacetonate) as a copper source and diethylzinc as a zinc source to deposit copper film. The selection of these precursors helps to prepare high-purity elemental copper through a reduction reaction, which can improve the electrical conductivity and thermal stability of the copper film.

[0142] 2. Innovative application of substrate materials: This method deposits copper thin films on BF33 glass substrates. The use of this substrate expands the application range of atomic layer deposition technology, making it possible to grow high-quality metal films on non-traditional semiconductor or metal substrates.

[0143] 3. Improvement of film quality: The morphology and uniformity of the copper film samples prepared by this method were tested and analyzed by scanning electron microscopy (SEM). The results showed that the copper film prepared by this method has good morphology and uniformity. This shows that this method can grow high-quality copper films on glass substrates, which is crucial for improving the electrical and mechanical properties of copper films.

[0144] 4. Precise control of film properties: This method can control the growth of copper film at the atomic level by precisely controlling the introduction time of the precursor and the carrier gas purge time, thereby obtaining a copper film with the desired thickness and excellent uniformity. This precise control method provides more design freedom and performance optimization space for the further application of the film.

[0145] 5. Improve production efficiency and reduce costs: Since the atomic layer deposition processing technology used in this method has the characteristics of self-limiting growth, it can reduce material waste, improve the production efficiency of copper films, and reduce the production cost of copper films.

[0146] 6. Environmental friendliness: The precursors and atomic layer deposition processes used in this method are relatively environmentally friendly. Compared with traditional physical vapor deposition and chemical vapor deposition molding methods, this method reduces the use and emissions of harmful chemicals and meets the environmental protection requirements of modern industrial production.

[0147] In summary, the embodiment of the present application provides a method for depositing and growing a copper thin film on a glass substrate. This method not only improves the quality and performance of the copper thin film, but also broadens its application scope. In addition, this method also has good economic and environmental benefits during actual use.

[0148] 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 copper thin film on a glass substrate surface, the method comprising: Pre-treating the glass substrate to obtain a pre-treated substrate; Using a copper source to perform a first atomic layer deposition treatment on the pretreated substrate under an inert atmosphere to obtain a rough substrate containing a rough copper film; The rough substrate containing the rough copper film is subjected to a second atomic layer deposition treatment using a zinc source under an inert gas atmosphere, so that the rough copper film undergoes a reduction reaction to obtain a glass substrate containing a copper film.

2. According to the method described in claim 1, the first atomic layer deposition process includes a first heating section and a copper source pulse section, the terminal temperature of the first heating section is 150°C to 200°C, and the pulse time of the copper source pulse section is 0.1s to 10.0s.

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 20s, the temperature of the first carrier gas purge section is 75°C to 85°C, and the carrier gas flow rate of the first carrier gas purge section is 10sccm to 150sccm.

4. According to the method described in claim 1, the second atomic layer deposition process includes a second heating section and a zinc source pulse section, the terminal temperature of the second heating section is 150°C to 200°C, and the pulse time of the zinc source pulse section is 0.01s to 10.0s.

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 0.1s to 20s, 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 copper source is 60° C. to 100° C.; and / or The temperature of the zinc source is 15°C to 30°C.

8. The method according to claim 1, wherein the type of the copper source comprises at least one of the following: copper sulfide, basic copper carbonate and bis(hexafluoroacetylacetonate)copper; and / or The zinc source includes at least one of the following: zinc oxide, zinc chloride and diethyl zinc.

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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