Initiation type molecular layer deposition method and regioselective deposition regulation and control method

Abstract

The invention discloses an initiation type molecular layer deposition method and a regioselective deposition regulation and control method. The initiation type molecular layer deposition method comprises the following steps: surface activation: placing a substrate in a reaction cavity, and forming a reaction site on the surface of the substrate by using plasma; a monomer is introduced into the reaction cavity, and the monomer acts on the reaction sites and deposits on the surface of the substrate to form a film layer; wherein the monomers comprise a first type of monomers and a second type of monomers, an active group of the first type of monomers comprises at least one double bond, and the second type of monomers comprise siloxane monomers without vinyl and silazane monomers without vinyl; and repeating the steps of surface activation and deposition in sequence until a film with a target thickness is obtained. According to the initiation type molecular layer deposition method, the film layer is prepared for multiple times, high-precision control over the thickness of the thin film is achieved, and the method is suitable for multiple monomers, simple in process and high in compatibility.

Description

Technical Field

[0001] The present application relates to the technical field of integrated circuit nano-manufacturing, and in particular to an induced molecular layer deposition method and a regional selective deposition control method. Background Art

[0002] Over the past half century, Moore's Law has been the core principle driving the rapid development of the semiconductor industry. This law has driven the continuous advancement of technology nodes. However, as the integrated circuit manufacturing process advances to 5nm or even more advanced technology nodes, the continuation of Moore's Law is limited by existing technologies. The traditional "top-down" patterning process that relies on lithography faces the dual challenges of pattern resolution and edge alignment. In response to the above problems, the development of a deposition method with a "self-alignment" effect is expected to achieve "bottom-up" patterning, which has good application prospects. However, most of the current deposition methods have difficulty in achieving high-precision control of the thickness of the film layer during the preparation of the polymer film layer, and the film is still thicker; or the film thickness can be controlled with high precision, but the types of polymers are limited. Therefore, it is urgent to study a thin film deposition method that can control the thickness with high precision and high compatibility. Summary of the invention

[0003] The present application discloses an induced molecular layer deposition method and a regional selective deposition control method, which can control the thickness of a thin film with high precision, have a simple process and high applicability.

[0004] In order to achieve the above objectives, this application provides the following technical solutions: In a first aspect, an embodiment of the present application provides an initiated molecular layer deposition method, comprising: Surface activation: placing the substrate in a reaction chamber and using plasma to form reaction sites on the substrate surface; Deposition: introducing monomers into the reaction chamber, the monomers reacting with the reaction sites and depositing on the surface of the substrate to form a film layer; wherein the monomers include first-type monomers and second-type monomers, the active groups of the first-type monomers include at least one double bond, and the second-type monomers include siloxane monomers without vinyl groups and silazane monomers without vinyl groups; The surface activation and the deposition steps are repeated sequentially until a thin film of target thickness is obtained.

[0005] The present application uses plasma to first form reaction sites on the surface of the substrate, and then allows the monomer to act on the reaction sites and deposit on the surface of the substrate to form a film layer. In the process of plasma treatment to form reaction sites, the amount of reaction sites formed each time can be controlled according to the plasma power, and then according to the time of passing the monomer, the thickness of the film layer deposited each time can be controlled, that is, a self-limiting reaction. It should be noted that the film layer deposited each time can be a monolayer molecule or a multilayer molecule, depending on the time and amount of the monomer. After a single film layer is formed, the film layer is in a relatively stable state, and its surface is no longer reactive. If the film layer needs to be deposited further, the surface of the previous film layer needs to be treated with plasma again to generate reaction sites, and the monomer is passed through, and the subsequent film layer is deposited to obtain a film of target thickness. Since the present application can achieve the deposition of a monolayer molecule, the film thickness control at the molecular level can be achieved. It can be understood that after a single film layer is formed and stabilized, continuing to pass the monomer will not react, that is, the thickness of the film layer obtained by the previous sequence will not be increased. Therefore, the method of the present application can achieve effective control of the film thickness, and the deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers without double bonds, thereby adapting to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a film of target thickness can be achieved.

[0006] In some embodiments, when the monomer is the first type of monomer, the monomer reacts with the reaction site and is deposited on the surface of the substrate to form a film layer, including: The first type of monomers are connected to the reaction sites and undergo a self-polymerization reaction, and are deposited on the surface of the substrate to form a polymer film layer.

[0007] The present application utilizes plasma to first form reaction sites on the surface of the substrate, and then connects the polymerizable monomers to the reaction sites and activates the self-polymerization reaction of the polymerizable monomers to form a polymer film layer.

[0008] In some embodiments, when the monomer is the second type of monomer, the monomer reacts with the reaction site and is deposited on the surface of the substrate to form a film layer, including: The reaction sites adsorb the second type of monomers and deposit them on the surface of the substrate to form a film layer.

[0009] The present application utilizes plasma to first form reaction sites on the substrate surface, and then allows the reaction sites to adsorb the second type of monomer, that is, a film layer can be deposited on the substrate surface by physical adsorption.

[0010] In some embodiments, the thickness of the film is greater than or equal to 0.5 angstroms. The film deposition method of the present application achieves angstrom-level control of film thickness, and each deposition cycle can achieve the growth of a polymer film layer of the same thickness, which has certain technical advantages.

[0011] In some embodiments, the method for forming the reaction site includes: performing plasma treatment on the surface of the substrate, or introducing an initiator into the reaction chamber and performing plasma treatment on the initiator. The present application forms high-energy particles on the surface of the substrate by plasma treatment, or generates free radicals on the surface of the substrate by plasma initiation initiator, and the high-energy particles or free radicals react with the monomer and are deposited on the surface of the substrate to form a film layer, thereby achieving deposition of the film layer.

[0012] In some embodiments, the initiator includes one or more of 2-hydroxy-2-methylphenylacetone, azo compounds, peroxide compounds, perfluorooctanesulfonyl fluoride, isobutyl phosphine and triethylamine.

[0013] In some embodiments, the first type of monomers includes one or more of olefin monomers containing carbonyl groups, styrene monomers, olefin monomers containing amides, siloxane monomers containing vinyl groups, and silazane monomers containing vinyl groups. This indicates that the deposition method of the present application can achieve polymerization deposition of a variety of monomers with double bonds, and has strong compatibility.

[0014] In a second aspect, the present application provides a method for regulating regional selective deposition, including: Surface activation: placing a substrate in a reaction chamber and using plasma to form reaction sites on the surface of the substrate; wherein the substrate comprises a first surface and a second surface, the first surface is made of a transition metal or a transition metal oxide, and the second surface is made of a non-transition metal or a non-transition metal oxide; Deposition: introducing monomers into the reaction chamber, the monomers reacting with the reaction sites and depositing on the surface of the substrate to form a film layer; wherein the monomers include first-type monomers and second-type monomers, the active groups of the first-type monomers include at least one double bond, and the second-type monomers include siloxane monomers without vinyl groups and silazane monomers without vinyl groups; Etching: etching and removing the film layer on the first surface; The surface activation, deposition and etching steps are repeated in sequence until a thin film of target thickness is obtained on the second surface.

[0015] The present application uses plasma to first form reaction sites on the surface of a substrate having a first surface and a second surface of different materials, and then allows the monomer to act on the reaction site and deposit on the substrate surface to form a film layer, and adds an etching process to achieve the regional selective deposition effect of the film. In the process of plasma treatment to form the reaction site, the amount of reaction sites formed each time can be controlled according to the plasma power, and then according to the time of passing the monomer, the thickness of the film layer deposited each time can be controlled, that is, a self-limiting reaction. It should be noted that the film layer deposited each time can be a monolayer molecule or a multilayer molecule, depending on the time and amount of the monomer. After a single film layer is formed, the film layer is in a relatively stable state, and its surface is no longer reactive. If the film layer needs to be deposited further, the surface of the previous film layer needs to be treated with plasma again to generate reaction sites, and the monomer is passed through, and the subsequent film layer is deposited to obtain a film of target thickness. Since the present application can achieve the deposition of a monolayer molecule, the film thickness control at the molecular level can be achieved. It can be understood that after a single film layer is formed and stabilized, continuing to pass the monomer will not react, that is, the thickness of the film layer obtained by the previous sequence will not be increased. Therefore, the method of the present application can achieve effective control of the film thickness, and the deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers not containing double bonds, thereby adapting to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a film of target thickness can be achieved. In addition, due to the different materials of the first surface and the second surface, the deposition rate of the monomer on the second surface is higher, and the deposition will be regionally selective. Moreover, due to the chemical properties of the material of the first surface, the film layer on the first surface is more easily etched, so the etching will also be regionally selective. By adding an etching step after each film layer deposition, the film layer on the first surface can be removed, thereby exposing the first surface again, and finally achieving the deposition of a film of target thickness on the second surface of the substrate.

[0016] In some embodiments, the thickness of the film is greater than or equal to 0.5 angstroms. The film deposition method of the present application achieves angstrom-level control of film thickness, and each deposition cycle can achieve the growth of a polymer film layer of the same thickness, which has certain technical advantages.

[0017] In some embodiments, the method for forming the reaction site includes: performing plasma treatment on the surface of the substrate, or introducing an initiator into the reaction chamber and performing plasma treatment on the initiator. The present application forms sites to be reacted on the surface of the substrate by plasma treatment, or generates free radicals on the surface of the substrate by plasma initiation, and high-energy particles or free radical monomers act and deposit on the surface of the substrate to form a film layer, thereby achieving deposition of the film layer.

[0018] In some embodiments, the initiator includes one or more of 2-hydroxy-2-methylphenylacetone, azo compounds, peroxide compounds, perfluorooctanesulfonyl fluoride, isobutyl phosphine and triethylamine.

[0019] In some embodiments, the first type of monomers includes one or more of olefin monomers containing carbonyl groups, styrene monomers, olefin monomers containing amides, siloxane monomers containing vinyl groups, and silazane monomers containing vinyl groups. This indicates that the deposition method of the present application can achieve polymerization and deposition of multiple monomers and has strong compatibility.

[0020] In some embodiments, the monomer has a deposition selectivity of greater than 90% on the second surface; The deposition selectivity c is: c=(ba) / (b+a), wherein a represents the deposition thickness of the thin film on the first surface, and b represents the deposition thickness of the thin film on the second surface.

[0021] In some embodiments, the regional selective deposition regulation method also includes: in at least one process of forming the film layer, using one of the induced chemical vapor deposition method, the atomic layer deposition method, the molecular layer deposition method or the plasma enhanced chemical vapor deposition method to replace the surface activation and the deposition steps to form the film layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 A schematic diagram of a process of an initiated molecular layer deposition method provided in an embodiment of the present application; Figure 2 A schematic diagram of a process flow of a regional selective deposition control method provided in an embodiment of the present application; Figure 3 A schematic diagram of a process of regional selective deposition of a thin film provided in an embodiment of the present application; Figure 4 A schematic diagram of mass change of a quartz crystal microbalance (QCM) during a thin film area selective deposition process provided in an embodiment of the present application; Figure 5 A SEM image of a thin film after regional selective deposition provided in an embodiment of the present application; Figure 6 AFM three-dimensional image and two-dimensional image of a film region selectively deposited after a first surface of the film having a strip-shaped structure is provided in an embodiment of the present application; Figure 7 An AFM two-dimensional image of a thin film region with a circular structure on the first surface after selective deposition and a height schematic diagram of the first surface and the second surface after deposition provided in an embodiment of the present application; Icon: 1. Substrate; 11. First surface; 12. Second surface; 2. Film layer. DETAILED DESCRIPTION

[0023] Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application. In the description of the embodiments of this application, unless otherwise specified, " / " means or, for example, A / B can mean A or B; "and / or" in the text is only a description of 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. In addition, in the description of the embodiments of this application, "multiple" means two or more than two.

[0024] The terms "first" and "second" are used for descriptive purposes only and should not be understood as suggesting or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the embodiments of the present application, unless otherwise specified, "multiple" means two or more.

[0025] The embodiments of the present application provide an induced molecular layer deposition method and a regional selective deposition control method, which can control the film thickness with high precision and high compatibility. The device prepared by this method has good reliability and durability.

[0026] In a first aspect, an embodiment of the present application provides an induced molecular layer deposition method, the deposition method comprising the following steps: S101, surface activation: placing the substrate in a reaction chamber, and forming reaction sites on the surface of the substrate using plasma; S102, deposition: introducing monomers into the reaction chamber, the monomers react with the reaction sites and are deposited on the substrate surface to form a film layer; wherein the monomers include a first type of monomer and a second type of monomer, the active group of the first type of monomer includes at least one double bond, and the second type of monomer includes a siloxane monomer that does not contain a vinyl group and a silazane monomer that does not contain a vinyl group; S103, repeating the surface activation and deposition steps in sequence until a film of target thickness is obtained.

[0027] The present application uses plasma to first form reaction sites on the surface of the substrate, and then allows the monomer to act on the reaction sites and deposit on the surface of the substrate to form a film layer. In the process of plasma treatment to form reaction sites, the amount of reaction sites formed each time can be controlled according to the plasma power, and then according to the time of passing the monomer, the thickness of the film layer deposited each time can be controlled, that is, a self-limiting reaction. It should be noted that the film layer deposited each time can be a monolayer molecule or a multilayer molecule, depending on the time and amount of the monomer. After a single film layer is formed, the film layer is in a relatively stable state, and its surface is no longer reactive. If the film layer needs to be deposited further, the surface of the previous film layer needs to be treated with plasma again to generate reaction sites, and the monomer is passed through, and the subsequent film layer is deposited to obtain a film of target thickness. Since the present application can achieve the deposition of a monolayer molecule, the film thickness control at the molecular level can be achieved. It can be understood that after a single film layer is formed and stabilized, continuing to pass the monomer will not react, that is, the thickness of the film layer obtained by the previous sequence will not be increased. Therefore, the method of the present application can achieve effective control of the film thickness, and the deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers without double bonds, thereby adapting to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a film of target thickness can be achieved.

[0028] Specifically, Figure 1 A schematic diagram of a process for inducing molecular layer deposition provided in an embodiment of the present application, referring to Figure 1 The initiated molecular layer deposition method comprises the following steps: (1) Surface activation: First, place the substrate in a reaction chamber, then use plasma to treat the substrate surface and form reaction sites on the substrate surface. It should be noted that the reaction sites include free radicals and high-energy particles.

[0029] (2) Deposition: After the reaction sites are formed on the substrate surface, monomers are introduced into the reaction chamber. Under the action of the reaction sites, the monomers are deposited on the substrate surface to form a film layer. The monomers include a first type of monomer and a second type of monomer. The active group of the first type of monomer includes at least one double bond. The second type of monomer includes a siloxane monomer that does not contain a vinyl group and a silazane monomer that does not contain a vinyl group. Due to the limited reaction sites on the substrate surface and the limited time for introducing the monomers, the monomers only react to a limited extent on the substrate surface and automatically stop reacting after a film layer of a certain thickness is produced, i.e., a self-limiting reaction.

[0030] In some embodiments, when the monomer is a first type monomer (the active group includes at least one double bond), the monomer acts on the reaction site and is deposited on the surface of the substrate to form a film layer, including: the first type monomer is connected to the reaction site and undergoes a self-polymerization reaction, and is deposited on the surface of the substrate to form a polymer film layer. Specifically, under the action of the reaction site, the active group of the polymerizable first type monomer breaks open, one end of the polymerizable first type monomer is connected to the reaction site on the surface of the substrate, and the other end undergoes a self-polymerization reaction and is deposited on the surface of the substrate. That is, the present application can connect the polymerizable monomer to the reaction site and activate the self-polymerization reaction of the polymerizable monomer to form a polymer film layer, thereby realizing the polymerization deposition of the monomer containing a double bond.

[0031] In some embodiments, when the monomer is a second type of monomer (a vinyl-free siloxane monomer and a vinyl-free silazane monomer), the monomer reacts with the reaction site and is deposited on the surface of the substrate to form a film layer, including: the reaction site adsorbs the second type of monomer, and deposits the film layer on the surface of the substrate. Specifically, the reaction site adsorbs the second type of monomer and deposits it on the surface of the substrate by physical adsorption. After the first film layer is deposited, when the plasma treatment is performed again, the structure of the first deposited film layer will be affected, that is, the film layer will be converted into a corresponding inorganic oxide film layer or an inorganic nitride film layer. At the same time, during the plasma treatment process, for example, the CC bond of the monomer will break and open, and link with other monomers, thereby forming a polymer film layer. Similarly, subsequent deposition cycles will affect the structure of the film layer deposited last time, and ultimately obtain inorganic films and polymer films of target thickness. Therefore, the method of the present application can not only prepare polymer films, but also prepare inorganic films.

[0032] (3) The above-mentioned surface activation and deposition steps are repeated in sequence to obtain a multilayer film layer, and the deposition of the film layer is stopped according to actual needs to obtain a film of target thickness.

[0033] The triggered molecular layer deposition method of the embodiment of the present application achieves high-precision control of the final film thickness by preparing the film layer multiple times, and is applicable to a variety of polymerizable monomers containing double bonds and monomers not containing double bonds. The process is simple and the compatibility is high.

[0034] It should be noted that the triggered molecular layer deposition method of the embodiment of the present application can achieve precise control of the internal components of the thin film, that is, it can achieve that the components of each film layer in the thin film are the same or different. Exemplarily, the first film layer in the thin film is polymerized by polymerizable monomer A, the second film layer is polymerized by polymerizable monomer B, the third film layer is polymerized by polymerizable monomer C, and the fourth film layer is polymerized by polymerizable monomer D. Of course, each polymer film layer in the thin film can also be polymerized by the same polymerizable monomer. In addition, the method of the present application can not only prepare polymer films of different polymer film layers, but also prepare films composed of inorganic film layers and polymer film layers.

[0035] It should be noted that after each surface activation step and each deposition step, a gas purge step may be added to remove excess unreacted initiator, free radicals, by-products, etc.

[0036] In some embodiments, the thickness of the film is greater than or equal to 0.5 angstroms. Exemplarily, the thickness of the film can be 0.5 angstroms, 1 angstroms, 5 angstroms, 15 angstroms, 18 angstroms, 20 angstroms, 100 angstroms, 124 angstroms, 500 angstroms, 542 angstroms, 1000 angstroms, etc., and the specific value is not limited. The deposition method of the film of the embodiment of the present application realizes angstrom-level control of the film thickness, and each deposition cycle can achieve the growth of the film layer of the same thickness, which has certain technical advantages.

[0037] In some embodiments, the method of forming the reaction sites includes: performing plasma treatment on the surface of the substrate, or introducing an initiator into a reaction chamber and performing plasma treatment on the initiator.

[0038] Specifically, the reaction sites include free radicals and high-energy particles. The generation method of high-energy particles may include: treating the surface of the substrate by plasma to generate high-energy particles on the surface of the substrate. These high-energy particles can adsorb monomers, thereby promoting the subsequent self-polymerization reaction of the monomers or promoting the physical deposition process of the monomers. The generation method of free radicals is: treating the initiator by plasma to cause the initiator to crack and generate free radicals, which can adsorb monomers and further induce the self-polymerization reaction of the monomers or promote the physical deposition process of the monomers.

[0039] In some embodiments, the initiator includes one or more of 2-hydroxy-2-methylphenylacetone, azo compounds, peroxide compounds, perfluorooctanesulfonyl fluoride, isobutylphosphine and triethylamine. Among them, the azo compound is one or more of azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN) or azodimethylformamide (ADMA). The peroxide compound is di-tert-amyl peroxide (Di- tert -amyl peroxide, TAPO), di-tert-butyl peroxide ( Tert -butylperoxide, TBPO), tert-butyl peroxybenzoate ( Tert -butyl peroxybenzoate, TBPOB) or benzoyl peroxide (Benzoyl peroxide, BPO) or one or more.

[0040] In some embodiments, the first monomer includes one or more of olefin monomers containing carbonyl groups, styrene monomers, olefin monomers containing amides, vinyl-containing siloxane monomers, and vinyl-containing silazane monomers. The olefin monomers containing carbonyl groups are one or more of acrylic acid (AA), methyl methacrylate (MAA), glyceryl methacrylate (GMA), ethylene glycol diacrylate (EGDA), hydroxyethylmethacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA), or 1H, 1H, 2H, 2H-perfluorodecyl acrylate (PFDA). The vinyl-containing siloxane monomer is one or more of 1, 3, 5-trivinyl-1, 3, 5-trimethylcyclotrisiloxane (1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane, V3D3), 2, 4, 6, 8-tetravinyl-2, 4, 6, 8-tetramethylcyclotetrasiloxane (1, 3, 5, 7-tetravinyl-1, 3, 5, 7-tetramethylcyclotetrasiloxane, V4D4) or hexavinyldisi-loxane (Hexavinyldisi-loxane, HVDSO). The vinyl-containing silazane monomer is one or more of 1, 3, 5-trivinyl-1, 3, 5-trimethylcyclotrisilazane (1, 3, 5-trivinyl-1, 3, 5-trimethylcyclotrisilazane, V3N3) or 1, 3,5, 7-tetravinyl-1, 3, 5, 7-tetramethyl-cyclotetrasilazane (1, 3, 5, 7-tetravinyl-1, 3, 5, 7-tetramethyl-cyclotetrasilazane, V4N4). The styrene monomer is one or more of vinylbenzene (Styrene, S), divinylbenzene (DVB), pentafluorophenyl methacrylate (Pentafluorophenyl methacrylate, FM) or dimethylaminomethylstyrene (Dimethylaminomethylstyrene, DMAMS).The olefin monomer with amide is one or more of acrylamide (Acrylamide, AAm), N,N-diethylacrylamide (N,N-Diethylacrylamide, DEAAm) or N,N-dimethylacrylamide (N,N-Dimethylacrylamide, DMAAm). This indicates that the deposition method of the present application can realize the polymerization deposition of various monomers with double bonds, and has strong compatibility.

[0041] In a second aspect, the present application provides a method for regulating regional selective deposition, comprising the following steps: S201, surface activation: placing a substrate in a reaction chamber, and forming reaction sites on the surface of the substrate using plasma; wherein the substrate comprises a first surface and a second surface, the material of the first surface is a transition metal or a transition metal oxide, and the material of the second surface is a non-transition metal or a non-transition metal oxide; S202, deposition: introducing monomers into the reaction chamber, the monomers react with the reaction sites and are deposited on the substrate surface to form a film layer; wherein the monomers include a first type of monomer and a second type of monomer, the active group of the first type of monomer includes at least one double bond, and the second type of monomer includes a siloxane monomer that does not contain a vinyl group and a silazane monomer that does not contain a vinyl group; S203, etching: etching to remove the film layer on the first surface; S204, repeating the surface activation, deposition, and etching steps in sequence until a thin film of target thickness is obtained on the second surface.

[0042] The present application uses plasma to first form reaction sites on the surface of a substrate having a first surface and a second surface of different materials, and then allows the monomer to act on the reaction site and deposit on the substrate surface to form a film layer, and adds an etching process to achieve the regional selective deposition effect of the film. In the process of plasma treatment to form the reaction site, the amount of reaction sites formed each time can be controlled according to the plasma power, and then according to the time of passing the monomer, the thickness of the film layer deposited each time can be controlled, that is, a self-limiting reaction. It should be noted that the film layer deposited each time can be a monolayer molecule or a multilayer molecule, depending on the time and amount of the monomer. After a single film layer is formed, the film layer is in a relatively stable state, and its surface is no longer reactive. If the film layer needs to be deposited further, the surface of the previous film layer needs to be treated with plasma again to generate reaction sites, and the monomer is passed through, and the subsequent film layer is deposited to obtain a film of target thickness. Since the present application can achieve the deposition of a monolayer molecule, the film thickness control at the molecular level can be achieved. It can be understood that after a single film layer is formed and stabilized, continuing to pass the monomer will not react, that is, the thickness of the film layer obtained by the previous sequence will not be increased. Therefore, the method of the present application can achieve effective control of the film thickness, and the deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers not containing double bonds, thereby adapting to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a film of target thickness can be achieved. In addition, due to the different materials of the first surface and the second surface, the deposition rate of the monomer on the second surface is higher, and the deposition will be regionally selective. Moreover, due to the chemical properties of the material of the first surface, the film layer on the first surface is more easily etched, so the etching will also be regionally selective. By adding an etching step after each film layer deposition, the film layer on the first surface can be removed, thereby exposing the first surface again, and finally achieving the deposition of a film of target thickness on the second surface of the substrate.

[0043] Specifically, Figure 2 A schematic diagram of a process for a regional selective deposition control method provided in an embodiment of the present application, Figure 3 A schematic diagram of a process of regional selective deposition of a thin film provided in an embodiment of the present application. Figure 2 and Figure 3 , the method for regulating the regional selective deposition of a thin film comprises the following steps: (1) Surface activation: First, the substrate 1 is placed in a reaction chamber, and then the surface of the substrate 1 is treated with plasma to form reaction sites on the surface of the substrate 1. The substrate 1 includes a first surface 11 and a second surface 12. The material of the first surface 11 is a transition metal or a transition metal oxide, such as cobalt, copper, iron, nickel, tungsten, cobalt oxide, copper oxide, etc. The material of the second surface 12 is a non-transition metal or a non-transition metal oxide, such as magnesium, aluminum oxide, zinc oxide, etc., and may also include silicon dioxide, silicon carbide, nitride, sulfide, etc., and may also include silicon oxycarbide, gold, and non-valence-changing metal oxides.

[0044] (2) Deposition: After the reaction sites are formed on the surface of the substrate, monomers are introduced into the reaction chamber. Under the action of the reaction sites, the monomers are deposited on the surface of the substrate to form a film layer. The monomers include a first type of monomer and a second type of monomer. The active group of the first type of monomer includes at least one double bond. The second type of monomer includes a siloxane monomer that does not contain a vinyl group and a silazane monomer that does not contain a vinyl group. Due to the limited reaction sites on the surface of the substrate 1 and the limited time for introducing the monomers, the monomers only react to a limited extent on the surface of the substrate 1 and automatically stop reacting after a film layer 2 of a certain thickness is produced, i.e., a self-limiting reaction.

[0045] In some embodiments, when the monomer is a first type of monomer (the active group includes at least one double bond), after the surface activation step and before the deposition step, the regional selective deposition control method further includes: introducing a co-oxidant into the reaction chamber, which is used to cause the first type of monomer to undergo a destructive reaction after the first type of monomer is introduced to reduce the self-polymerization reaction of the first type of monomer on the first surface 11. Specifically, the material of the first surface 11 will catalyze the co-oxidant to react with the first type of monomer introduced subsequently, and the vinyl epoxidation of the first type of monomer will occur, resulting in the consumption of the active group that should have participated in the self-polymerization reaction, thereby reducing the self-polymerization reaction of the first type of monomer on the first surface 11, that is, reducing the deposition of the polymer film layer on the first surface 11, thereby causing regional selective deposition. In some embodiments, the co-oxidant includes one or more of peroxide, oxygen, ozone and nitrous oxide. Among them, the peroxide includes di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxide, hydrogen peroxide, etc.

[0046] In some embodiments, when the monomer is a second type of monomer (non-vinyl siloxane monomer and non-vinyl silazane monomer), due to the different materials of the first surface 11 and the second surface 12, under the catalytic action of the material of the first surface 11, the second type of monomer (non-vinyl siloxane monomer and non-vinyl silazane monomer) will undergo a ring-opening reaction, thereby occupying the reaction sites on the first surface 11, so the deposition rate of the monomer on the second surface 12 is higher, and the deposition exhibits regional selectivity.

[0047] It should be noted that when the first type of monomers introduced are vinyl-containing siloxane monomers and non-vinyl-containing silazane monomers, since the monomers will also undergo a ring-opening reaction, resulting in selective deposition, it is not necessary to add a co-oxidant.

[0048] (3) Etching: Etching the film layer 2 on the surface of the substrate 1 until the film layer 2 on the first surface 11 is completely etched away. Etching includes dry etching and wet etching. It should be noted that due to the different materials of the first surface 11 and the second surface 12, the film layer 2 on the first surface 11 is more easily etched, so the etching will also show regional selectivity. Removing the film layer 2 deposited on the first surface 11 can further expose the first surface 11, so that the selective deposition effect can continue. Therefore, the etching step can increase the thickness difference between the first surface 11 and the second surface 12, and improve the deposition selectivity.

[0049] It should be noted that when only the second type of monomers (non-vinyl siloxane monomers and non-vinyl silazane monomers) are included, after the first film deposition and etching, when plasma treatment is performed again, the structure of the first deposited film will be affected, that is, the film will be converted into a corresponding oxide film or nitride film. At the same time, during the plasma treatment process, for example, the CC bond of the monomer will break and open, and link with other monomers, thereby forming a polymer film. Similarly, subsequent deposition cycles will affect the structure of the film deposited last time, and ultimately obtain inorganic films and polymer films of target thickness. Therefore, the method of the present application can not only achieve regional selective deposition of polymer films, but also regional selective deposition of oxide films and nitride films.

[0050] (4) The above-mentioned surface activation, deposition and etching steps are performed in a cycle to obtain a multi-layer film layer, and the deposition of film layer 2 is stopped according to actual needs to obtain a film of target thickness.

[0051] The method for regulating the regional selective deposition of the thin film in the embodiment of the present application realizes the high-precision control of the regional selective deposition and thickness of the thin film by depositing multiple film layers and adopting the first surface 11 and the second surface 12 of different materials and the etching step of the film layer 2. The method is applicable to a variety of monomers (polymerizable monomers and monomers not containing double bonds), has a simple process and high compatibility, and can be widely used in electronics, optoelectronics, biomedicine and other fields.

[0052] It should be noted that the regional selective deposition control method of the thin film of the embodiment of the present application can achieve precise control of the internal components of the thin film, that is, it can achieve the same or different components of each film layer in the thin film. Exemplarily, the first film layer in the thin film is polymerized by polymerizable monomer A, the second film layer is polymerized by polymerizable monomer B, the third film layer is polymerized by polymerizable monomer C, and the fourth film layer is polymerized by polymerizable monomer D. Of course, each polymer film layer in the thin film can also be polymerized by the same monomer. In addition, the method of the present application can not only achieve regional selective deposition of polymer films of different polymer film layers, but also achieve regional selective deposition of thin films composed of oxide film layers, nitride film layers and polymer film layers.

[0053] It should be noted that after each surface activation, each deposition step and each etching step, a gas purge step may be added to remove excess unreacted initiators, free radicals, by-products, etc. The thickness of the film, the method of forming the reaction sites, the type of initiator and the type of monomer are the same as those of the first aspect and will not be described in detail.

[0054] Reference Figure 3 , the deposition selectivity of the monomer on the second surface 12 is greater than 90%; the deposition selectivity c is: c=(ba) / (b+a), where a represents the deposition thickness of the film on the first surface 11, and b represents the deposition thickness of the film on the second surface 12.

[0055] The method for regulating the regional selective deposition of a thin film in an embodiment of the present application also includes: in at least one process of forming a film layer, a film layer is formed by using an induced chemical vapor deposition method, an atomic layer deposition method, a molecular layer deposition method or a plasma enhanced chemical vapor deposition method to replace the surface activation and deposition steps.

[0056] As an exemplary description, in the process of forming the first film layer, the induced molecular layer deposition method as in the first aspect is adopted, in the process of forming the second film layer, the induced chemical vapor deposition method is adopted, and in the process of forming the third film layer, the plasma enhanced chemical vapor deposition method is adopted, finally obtaining a thin film of the target thickness.

[0057] As another exemplary explanation, in the formation process of the first and second film layers, the induced molecular layer deposition method of the first aspect is adopted, in the formation process of the third film layer, the atomic layer deposition method is adopted, in the formation process of the fourth film layer, the plasma enhanced chemical vapor deposition method is adopted, and in the formation process of the fifth film layer, the molecular layer deposition method is adopted, finally obtaining a thin film of the target thickness.

[0058] In order to further illustrate the present application, the following describes in detail a method for inducing molecular layer deposition of a thin film and a method for regulating regional selective deposition provided by the present application in combination with specific embodiments. Example 1

[0059] This embodiment is a method for regulating and controlling the regional selective deposition of a thin film, which specifically includes the following steps: (1) Surface activation: The patterned substrate is placed in a reaction chamber, and Ar plasma is used to activate the substrate surface for 1-60 s to form active sites of high-energy particles, followed by Ar gas purge for 5-180 s; wherein the material of the first surface is Co and the material of the second surface is SiO2.

[0060] (2) Deposition: 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3) is introduced into the reaction chamber as a polymerizable monomer for a time of 5-180 s, and a polymer film layer is deposited on the surface of the substrate, followed by Ar gas purge for 5-360 s.

[0061] (3) Repeat the surface activation and deposition steps 50 times in sequence until a film of target thickness is obtained on the second surface, which is a SiOC(H) film.

[0062] In Example 1, the reaction chamber temperature is set to 10-100° C., the substrate temperature is set to 0-80° C., and the power of the plasma power supply is set to 5-500 W. In addition, a heating jacket is used to heat the source bottle containing V3D3 and maintain it at 30-90° C. Example 2

[0063] This embodiment is a method for regulating and controlling the regional selective deposition of a thin film, which specifically includes the following steps: (1) Surface activation: Place the patterned substrate in the reaction chamber and add di-tert-butyl peroxide ( Tert -butylperoxide, TBPO) is used as an initiator and introduced into the reaction chamber together with Ar plasma for 1-60 s to generate free radicals on the substrate surface, and then Ar gas is used for purging for 5-180 s; wherein the material of the first surface is Co and the material of the second surface is SiO2.

[0064] (2) Deposition: 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3) is introduced into the reaction chamber as a polymerizable monomer for a time of 5-180 s, and a polymer film layer is deposited on the surface of the substrate, followed by Ar gas purge for 5-360 s.

[0065] (3) Repeat the surface activation and deposition steps 50 times in sequence until a film of target thickness is obtained on the second surface, which is a SiOC(H) film.

[0066] In Example 2, the reaction chamber temperature is set to 10-100°C, the substrate temperature is set to 0-80°C, and the power of the plasma power supply is set to 5-500W. In addition, the source bottles containing TBPO and V3D3 are heated and maintained at 20-80°C and 30-90°C respectively using a heating jacket. In Example 2, during the process of preparing the thin film, at least one polymer film layer is prepared by an induced chemical vapor deposition method. Example 3

[0067] This embodiment is a method for regulating and controlling the regional selective deposition of a thin film, which specifically includes the following steps: (1) Surface activation: The patterned substrate is placed in a reaction chamber, and Ar plasma is used to activate the substrate surface for 1-60 s to form active sites of high-energy particles, followed by Ar gas purge for 5-180 s; wherein the material of the first surface is Co and the material of the second surface is SiO2.

[0068] (2) Deposition: 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3) is introduced into the reaction chamber as a polymerizable monomer for a time of 5-180 s, and a polymer film layer is deposited on the surface of the substrate, followed by Ar gas purge for 5-360 s.

[0069] (3) Etching: The polymer film layer is plasma etched with O2 and Ar for 5-40 seconds until the polymer film layer on the first surface is completely removed, and then purged with Ar gas for 5-180 seconds.

[0070] (4) Repeating the surface activation, deposition, and etching steps 50 times in sequence until a film of target thickness is obtained on the second surface, which is a SiOC(H) film.

[0071] In Example 3, the reaction chamber temperature is set to 10-100°C, the substrate temperature is set to 0-80°C, and the power of the plasma power supply is set to 5-500 W. The flow rates of O2 and Ar during the etching process are set to 1-50 sccm and 1-20 sccm, respectively. In addition, a heating jacket is used to heat the source bottle containing V3D3 and maintain it at 30-90°C. Example 4

[0072] This embodiment is a method for regulating and controlling the regional selective deposition of a thin film, which specifically includes the following steps: (1) Surface activation: The patterned substrate is placed in a reaction chamber, and di-tert-butyl peroxide (TBPO) is introduced into the reaction chamber as an initiator together with Ar plasma for 1-60 s to generate free radicals on the substrate surface, and then Ar gas is used for purging for 5-180 s; wherein the material of the first surface is Co and the material of the second surface is SiO2.

[0073] (2) Deposition: 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3) is introduced into the reaction chamber as a polymerizable monomer for a time of 5-180 s, and a polymer film layer is deposited on the surface of the substrate, followed by Ar gas purge for 5-360 s.

[0074] (3) Etching: The polymer film layer is plasma etched with O2 and Ar for 5-40 seconds until the polymer film layer on the first surface is completely removed, and then purged with Ar gas for 5-180 seconds.

[0075] (4) Repeat the surface activation, deposition, and etching steps 90 times in sequence until a film of target thickness is obtained on the second surface, which is a SiOC(H) film.

[0076] In Example 4, the reaction chamber temperature is set to 10-100°C, the substrate temperature is set to 0-80°C, and the power of the plasma power supply is set to 5-500 W. The flow rates of O2 and Ar during the etching process are set to 1-50 sccm and 1-20 sccm, respectively. In addition, the source bottles containing TBPO and V3D3 are heated and maintained at 20-80°C and 30-90°C, respectively, using a heating jacket.

[0077] Example 5-Example 13

[0078] Examples 5 to 13 are respectively a method for regulating and controlling the regional selective deposition of a thin film. The steps of Examples 5 to 13 are the same as those of Example 4, and detailed information such as the materials used in each step are shown in Table 1.

[0079] Comparative Example 1 This comparative example is a method for regulating and controlling the regional selective deposition of a thin film, which specifically includes the following steps: placing a patterned substrate in a reaction chamber, passing p-xylene monomer (monomer without double bonds) into the reaction chamber for 1-60 s, and simultaneously initiating TBPO initiator to generate free radicals on the surface of the substrate by Ar plasma initiation, so as to deposit a polymer film on the surface of the substrate. The material of the first surface is Co, and the material of the second surface is SiO2.

[0080] Comparative Example 2 This comparative example is a method for regulating and controlling the regional selective deposition of a thin film, which specifically includes the following steps: placing a patterned substrate in a reaction chamber, introducing a TBPO initiator and a toluene monomer (a monomer without double bonds) into the reaction chamber simultaneously for 1-60 s, and simultaneously initiating the TBPO initiator to generate free radicals on the surface of the substrate by thermal initiation, so as to deposit a polymer film on the surface of the substrate. The material of the first surface is Co, and the material of the second surface is SiO2.

[0081] Comparative Example 3 This comparative example is a method for regulating the regional selective deposition of a thin film, which specifically includes the following steps: placing a patterned substrate in a reaction chamber, introducing a TBPO initiator and a p-xylene monomer (a monomer without double bonds) into the reaction chamber simultaneously for 1-60 s, and simultaneously initiating the TBPO initiator to generate free radicals on the substrate surface by photoinitiation, so as to deposit a polymer film on the substrate surface. The material of the first surface is Co, and the material of the second surface is SiO2.

[0082] Comparative Example 4 This comparative example is a method for regulating the regional selective deposition of a thin film, which specifically includes the following steps: placing a patterned substrate in a reaction chamber, introducing a TBPO initiator into the reaction chamber for 1-60 s, initiating the TBPO initiator to generate free radicals on the surface of the substrate by thermal initiation, and then introducing a propane monomer (a monomer without a double bond) to deposit on the surface of the substrate to form a polymer film layer, and repeating the above steps to form a polymer film. The material of the first surface is Co, and the material of the second surface is SiO2.

[0083] Table 1

[0084] It can be seen from Table 1 that compared with comparative examples 1-4, the deposition thickness of the film on the second surface in the embodiment of the present application is significantly greater than the deposition thickness on the first surface, indicating that the regional selective deposition control method of the embodiment of the present application can achieve selective deposition of the film on the second surface.

[0085] For the above-mentioned Examples 1-13, the film increments on the first surface and the second surface were respectively detected using an ellipsometer, and the test results are listed in Table 1. Since an etching step was added during the film deposition process in Examples 3-13, the deposition selectivity on the second surface was higher than 90%.

[0086] It should be noted that in this embodiment, a circulating water device is also used to control the substrate temperature of the reaction chamber and the bottom temperature of the quartz crystal microbalance to keep the two temperatures consistent. During the deposition process of the same batch of thin films, two quartz crystal microbalances are used to detect the film increments on the first surface and the second surface respectively. Figure 4A schematic diagram of the mass change of a quartz crystal microbalance during a thin film area selective deposition process provided in an embodiment of the present application. Figure 4 As shown, the quality difference between the thin films on the first surface and the second surface gradually widens with the increase in the number of deposition cycles, indicating that the thin film area selective deposition method of the embodiment of the present application can improve the deposition selectivity.

[0087] Figure 5 This is a SEM image of a thin film after area selective deposition provided in an embodiment of the present application. Figure 6 An embodiment of the present application provides an AFM three-dimensional image and a two-dimensional image after selective deposition of a thin film region with a strip-shaped structure on the first surface, wherein the dark area is the area of ​​the first surface of the strip-shaped structure, and the light area is the area of ​​the second surface. Figure 7 An AFM two-dimensional image of a thin film region with a circular structure on the first surface after selective deposition and a schematic diagram of the heights of the first surface and the second surface after deposition provided in an embodiment of the present application, wherein the dark area in the left image is the area of ​​the first surface with a circular structure, and the light area is the area of ​​the second surface; after selective deposition of the region in the right image, the heights of the first surface and the second surface are obtained according to the white line area in the left image, that is, the heights of the thin film growth area and the non-growth area.

[0088] In order to demonstrate the effect of the thin film area selective deposition method proposed in the embodiment of the present application, the embodiment is deposited on a patterned substrate prepared by photolithography, evaporation or magnetron sputtering, and the substrate after deposition is characterized by SEM. Figure 5 As shown, Figure 5 (a) shows the topography of the patterned substrate. Figure 5 (b) in the figure shows a local topography of a patterned substrate. The material of the first surface of the substrate is Co, and the material of the second surface is SiOC. After the thin film area selective deposition, the deposition thickness of the thin film on the first surface is 7.1nm, and the deposition thickness on the second surface is 13.8nm. This shows that the thin film area selective deposition method of the embodiment of the present application can improve the deposition selectivity.

[0089] like Figure 6 and Figure 7 As shown, the embodiment of the present application performs AFM characterization on the substrate after regional selective deposition of thin film. It can be seen from the figure that an obvious regional selective deposition effect is exhibited on the first surface and the second surface of the substrate, indicating that the regional selective deposition method of thin film in the embodiment of the application can improve the deposition selectivity.

[0090] Obviously, those skilled in the art can make various changes and modifications to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to include these modifications and variations.

Claims

1. A method for inducing molecular layer deposition, characterized in that: include: Surface activation: placing the substrate in a reaction chamber and using plasma to form reaction sites on the substrate surface; Deposition: introducing monomers into the reaction chamber, the monomers reacting with the reaction sites and depositing on the surface of the substrate to form a film layer; wherein the monomers include first-type monomers and second-type monomers, the active groups of the first-type monomers include at least one double bond, and the second-type monomers include siloxane monomers without vinyl groups and silazane monomers without vinyl groups; The surface activation and the deposition steps are repeated sequentially until a thin film of target thickness is obtained.

2. The method for initiating molecular layer deposition according to claim 1, characterized in that: When the monomer is the first type of monomer, the monomer acts on the reaction site and is deposited on the surface of the substrate to form a film layer, including: The first type of monomers are connected to the reaction sites and undergo a self-polymerization reaction, and are deposited on the surface of the substrate to form a polymer film layer.

3. The method for initiating molecular layer deposition according to claim 1, characterized in that: When the monomer is the second type of monomer, the monomer acts on the reaction site and is deposited on the surface of the substrate to form a film layer, including: The reaction sites adsorb the second type of monomers and deposit them on the surface of the substrate to form a film layer.

4. The method for initiating molecular layer deposition according to claim 1, characterized in that: The thickness of the film is greater than or equal to 0.5 angstroms.

5. The method for initiated molecular layer deposition according to claim 1, characterized in that: The method for forming the reaction site includes: performing plasma treatment on the surface of the substrate, or introducing an initiator into the reaction chamber and performing plasma treatment on the initiator.

6. The method for initiated molecular layer deposition according to claim 5, characterized in that: The initiator includes one or more of 2-hydroxy-2-methylphenylacetone, azo compounds, peroxide compounds, perfluorooctanesulfonyl fluoride, isobutyl phosphine and triethylamine.

7. The method for initiated molecular layer deposition according to claim 2, characterized in that: The first type of monomers include one or more of vinyl monomers containing carbonyl groups, styrene monomers, vinyl monomers containing amides, siloxane monomers containing vinyl groups, and silazane monomers containing vinyl groups.

8. A method for regulating regional selective deposition, characterized in that: include: Surface activation: placing a substrate in a reaction chamber and using plasma to form reaction sites on the surface of the substrate; wherein the substrate comprises a first surface and a second surface, the first surface is made of a transition metal or a transition metal oxide, and the second surface is made of a non-transition metal or a non-transition metal oxide; Deposition: introducing monomers into the reaction chamber, the monomers reacting with the reaction sites and depositing on the surface of the substrate to form a film layer; wherein the monomers include first-type monomers and second-type monomers, the active groups of the first-type monomers include at least one double bond, and the second-type monomers include siloxane monomers without vinyl groups and silazane monomers without vinyl groups; Etching: etching and removing the film layer on the first surface; The surface activation, deposition and etching steps are repeated in sequence until a thin film with a target thickness is obtained on the second surface.

9. The method for regulating and controlling regional selective deposition according to claim 8, characterized in that: The monomer has a deposition selectivity of greater than 90% on the second surface; The deposition selectivity c is: c=(ba) / (b+a), wherein a represents the deposition thickness of the thin film on the first surface, and b represents the deposition thickness of the thin film on the second surface.

10. The method for regulating and controlling regional selective deposition according to claim 8, characterized in that: The method for regulating the regional selective deposition of the thin film also includes: in at least one process of forming the film layer, using one of the induced chemical vapor deposition method, the atomic layer deposition method, the molecular layer deposition method or the plasma enhanced chemical vapor deposition method to replace the surface activation and the deposition steps to form the film layer.

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