A triggered atomic layer deposition method and a method for regulating area-selective deposition

Abstract

The present application discloses an initiation molecular layer deposition method and a method for regulating area-selective deposition. The initiation molecular layer deposition method comprises the following steps: surface activation: placing a substrate in a reaction chamber, and forming reaction sites on the surface of the substrate by using plasma; deposition: introducing monomers into the reaction chamber, and the monomers act on the reaction sites and deposit on the surface of the substrate 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 vinyl-free siloxane monomer and a vinyl-free silazane monomer; repeating the surface activation and deposition steps in sequence until a thin film with a target thickness is obtained. The initiation molecular layer deposition method of the present application realizes high-precision control of the thin film thickness by preparing the film layer multiple times, is applicable to various monomers, has a simple process and high compatibility.

Description

Technical Field

[0001] The present application relates to the field of integrated circuit nano - manufacturing technology, and particularly to an initiation - type atomic layer deposition method and a method for regulating area - selective deposition. Background Art

[0002] For the past half - century, Moore's Law has been the core principle driving the rapid development of the semiconductor industry, which has driven the continuous advancement of technology nodes. However, as the integrated circuit manufacturing process enters the 5nm and even more advanced technology nodes, the continuation of Moore's Law is restricted by existing technologies. The traditional "top - down" patterning process relying on lithography faces the dual challenges of pattern resolution and edge alignment. To address the above problems, developing a deposition method with a "self - alignment" effect is expected to achieve "bottom - up" patterning, with good application prospects. Currently, most deposition methods are difficult to achieve high - precision control of the film thickness during the preparation of polymer film layers, and there will still be cases where the prepared thin film is relatively thick; or they can achieve high - precision control of the film thickness, but the types of polymers are limited. Therefore, there is an urgent need to study a thin - film deposition method that can control the thickness with high precision and has high compatibility. Summary of the Invention

[0003] The present application discloses an initiation - type atomic layer deposition method and a method for regulating area - selective deposition, which can control the thickness of the thin film with high precision, have a simple process, and high applicability.

[0004] To achieve the above object, the present application provides the following technical solutions:

[0005] In a first aspect, an embodiment of the present application provides an initiation - type atomic layer deposition method, including:

[0006] Surface activation: placing a substrate in a reaction chamber and using plasma to form reaction sites on the surface of the substrate;

[0007] Deposition: introducing monomers into the reaction chamber, and the monomers react with the reaction sites and deposit to form a film layer on the surface of the substrate; 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 vinyl - free siloxane monomers and vinyl - free silazane monomers;

[0008] Sequentially repeat the surface activation and deposition steps until a thin film with a target thickness is obtained.

[0009] In this application, plasma is first used to form reaction sites on the substrate surface, and then monomers are allowed to act on the reaction sites and a film layer is deposited on the substrate surface. During the process of forming reaction sites by plasma treatment, the amount of reaction sites formed each time can be controlled according to the plasma power. Furthermore, according to the time of introducing monomers, the thickness of the film layer deposited each time can be controlled, that is, self-limiting reaction. It should be noted that the film layer deposited each time can be a single-layer molecule or multiple-layer molecules, which depends on the time and amount of introducing monomers. After a single film layer is formed, the film layer is in a relatively stable state and its surface no longer has reaction activity. If it is necessary to continue depositing the film layer, it is necessary to use plasma to treat the surface of the previous film layer again to generate reaction sites, introduce monomers, and deposit subsequent film layers to obtain a thin film with a target thickness. Since this application can achieve the deposition of single-layer molecules, that is, it can achieve film thickness control at the molecular level. It can be understood that after a single film layer is formed and stabilized, continuing to introduce monomers will not cause a reaction, that is, it will not increase the thickness of the previous obtained film layer. Therefore, the method of this application can effectively control the thickness of the thin film, and this deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers without double bonds, so as to adapt to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a thin film with a target thickness can be achieved.

[0010] In some embodiments, when the monomer is the first type of monomer, the monomer acts on the reaction sites and a film layer is deposited on the substrate surface, including:

[0011] The first type of monomer is connected to the reaction sites and undergoes a self-polymerization reaction to deposit a polymer film layer on the substrate surface.

[0012] This application uses plasma to first form reaction sites on the substrate surface, and then enables the polymerizable monomer to be connected to the reaction sites and activates the self-polymerization reaction of the polymerizable monomer to form a polymer film layer.

[0013] In some embodiments, when the monomer is the second type of monomer, the monomer acts on the reaction sites and a film layer is deposited on the substrate surface, including:

[0014] The reaction sites adsorb the second type of monomer to deposit a film layer on the substrate surface.

[0015] This application uses plasma to first form reaction sites on the substrate surface, and then enables 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.

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

[0017] In some embodiments, the method for forming the reaction sites 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. In the present application, high-energy particles are formed on the surface of the substrate through plasma treatment, or free radicals are generated on the surface of the substrate by plasma-initiated initiators. The high-energy particles or free radicals act on the monomers and deposit on the surface of the substrate to form a film layer, realizing the 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, isobutylphosphine, and triethylamine.

[0019] In some embodiments, the first type of monomers includes one or more of olefin monomers containing a carbonyl group, styrene monomers, olefin monomers containing an amide group, vinyl-containing siloxane monomers, and vinyl-containing silyl azide monomers. It shows that the deposition method of the present application can achieve the polymerization deposition of various monomers with double bonds and has strong compatibility.

[0020] In a second aspect, an embodiment of the present application provides a method for regulating area-selective deposition, including:

[0021] Surface activation: placing the substrate in a reaction chamber and using plasma to form reaction sites on the surface of the substrate; wherein, the substrate includes 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;

[0022] Deposition: introducing monomers into the reaction chamber, and the monomers act on the reaction sites and deposit on the surface of the substrate to form a film layer; wherein, the monomers include a first type of monomers and a second type of monomers, the active group of the first type of monomers includes at least one double bond, and the second type of monomers includes vinyl-free siloxane monomers and vinyl-free silyl azide monomers;

[0023] Etching: etching and removing the film layer on the first surface;

[0024] Sequentially repeat the surface activation, deposition, and etching steps until a thin film with a target thickness is obtained on the second surface.

[0025] This application utilizes plasma to first form reaction sites on the surface of a substrate with first and second surfaces of different materials, then allows monomers to act on the reaction sites and deposit a film layer on the substrate surface, and incorporates an etching process to achieve a region-selective deposition effect of the thin film. During the process of forming reaction sites by plasma treatment, the amount of reaction sites formed each time can be controlled according to the plasma power, and then, according to the time of introducing monomers, the thickness of the film layer deposited each time can be controlled, that is, self-limiting reaction. It should be noted that the film layer deposited each time can be a single-layer molecule or multiple-layer molecules, which depends on the time and amount of introducing monomers. After a single film layer is formed, the film layer is in a relatively stable state and its surface no longer has reaction activity. If it is necessary to continue depositing the film layer, it is necessary to use plasma to treat the surface of the previous film layer again to generate reaction sites, introduce monomers, and deposit the subsequent film layer to obtain a thin film with a target thickness. Since this application can achieve the deposition of single-layer molecules, that is, it can achieve film thickness control at the molecular level. It can be understood that after a single film layer is formed and stabilized, continuing to introduce monomers will not cause a reaction, that is, it will not increase the thickness of the previous obtained film layer. Therefore, the method of this application can effectively control the thickness of the thin film, and this deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers without double bonds, so as to adapt to the deposition of various film layers. By controlling the number of cycles, the deposition of a thin film with a target thickness can be achieved. In addition, due to the different materials of the first surface and the second surface, the deposition rate of monomers on the second surface is higher, and the deposition shows region selectivity. And 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 also shows region selectivity. Adding an etching step after each film layer deposition can remove the film layer on the first surface, thereby exposing the first surface again, and finally achieving the deposition of a thin film with a target thickness on the second surface of the substrate.

[0026] In some embodiments, the thickness of the thin film is greater than or equal to 0.5 angstroms. The deposition method of the thin film of this application achieves angstrom-level control of the thin film thickness, and the growth of a polymer film layer with the same thickness can be achieved in each deposition cycle, which has certain technical advantages.

[0027] 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 the reaction chamber and performing plasma treatment on the initiator. This application forms reaction sites to be reacted on the substrate surface through plasma treatment, or generates free radicals on the substrate surface through plasma-initiated initiators, and high-energy particles or free radical monomers act and deposit a film layer on the substrate surface to achieve the deposition of the film layer.

[0028] In some embodiments, the initiator includes one or more of 2-hydroxy-2-methylphenylacetone, azo compounds, peroxide compounds, perfluorooctanesulfonyl fluoride, isobutylphosphine, and triethylamine.

[0029] In some embodiments, the first type of monomers includes one or more of olefin monomers containing a carbonyl group, styrene monomers, olefin monomers containing an amide group, vinyl-containing siloxane monomers, and vinyl-containing silazane monomers. It shows that the deposition method of the present application can achieve the polymerization and deposition of multiple monomers and has strong compatibility.

[0030] In some embodiments, the deposition selectivity of the monomer on the second surface is greater than 90%;

[0031] The deposition selectivity c is: c = (b - a) / (b + a), where 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.

[0032] In some embodiments, the method for regulating area-selective deposition further includes: in at least one of the processes of forming the film layer, using one of the initiated chemical vapor deposition method, atomic layer deposition method, molecular layer deposition method, or plasma-enhanced chemical vapor deposition method to replace the steps of surface activation and deposition to form the film layer. Description of the Drawings

[0033] Figure 1 Flow schematic diagram of an initiated molecular layer deposition method provided by an embodiment of the present application;

[0034] Figure 2 Flow schematic diagram of a method for regulating area-selective deposition provided by an embodiment of the present application;

[0035] Figure 3 Process schematic diagram of area-selective deposition of a thin film provided by an embodiment of the present application;

[0036] Figure 4 Schematic diagram of the mass change of a quartz crystal microbalance (QCM) during the area-selective deposition of a thin film provided by an embodiment of the present application;

[0037] Figure 5 SEM image of a thin film after area-selective deposition provided by an embodiment of the present application;

[0038] Figure 6 3D and 2D AFM images of a thin film after area-selective deposition with a strip-shaped structure on the first surface provided by an embodiment of the present application;

[0039] Figure 7 The AFM two-dimensional image after the area-selective deposition of a thin film with a circular structure on the first surface provided by the embodiment of the present application, and the schematic diagram of the heights of the first surface and the second surface after deposition;

[0040] Icons: 1. Substrate; 11. First surface; 12. Second surface; 2. Film layer. Detailed implementation manners

[0041] Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application. Among them, in the description of the embodiments of the present application, unless otherwise specified, " / " means "or". For example, A / B may mean A or B; "and / or" in the text is only a description of the association relationship of the associated objects, indicating that there can be three relationships. For example, A and / or B may mean: A exists alone, A and B exist simultaneously, and B exists alone. In addition, in the description of the embodiments of the present application, "a plurality of" means two or more than two.

[0042] Among them, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as implying or suggesting relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the embodiments of the present application, unless otherwise specified, the meaning of "a plurality of" is two or more than two.

[0043] The embodiments of the present application provide an initiation molecular layer deposition method and an area-selective deposition control method, which can accurately control the film thickness with high compatibility. The devices prepared by this method have good reliability and durability.

[0044] In a first aspect, the embodiments of the present application provide an initiation molecular layer deposition method, and this deposition method includes the following steps:

[0045] S101. Surface activation: Place the substrate in the reaction chamber, and use plasma to form reaction sites on the substrate surface;

[0046] S102. Deposition: Introduce monomers into the reaction chamber. The monomers react with the reaction sites and deposit on the substrate surface to form a film layer. Among them, the monomers include a first type of monomer and a second type of monomer. The active groups of the first type of monomer include at least one double bond, and the second type of monomer includes vinyl-free siloxane monomers and vinyl-free silazane monomers;

[0047] S103. Sequentially repeat the surface activation and deposition steps until a thin film with a target thickness is obtained.

[0048] In this application, plasma is first used to form reaction sites on the surface of the substrate, and then monomers are allowed to act on the reaction sites and deposit on the surface of the substrate to form a film layer. During the process of forming reaction sites by plasma treatment, the amount of reaction sites formed each time can be controlled according to the plasma power, and then according to the time of introducing monomers, the thickness of the film layer deposited each time can be controlled, that is, self-limiting reaction. It should be noted that the film layer deposited each time can be a single-layer molecule or multiple-layer molecules, which depends on the time and amount of introducing monomers. After a single film layer is formed, the film layer is in a relatively stable state and its surface no longer has reaction activity. If it is necessary to continue depositing the film layer, it is necessary to use plasma to treat the surface of the previous film layer again to generate reaction sites, introduce monomers, and deposit the subsequent film layer to obtain a thin film with a target thickness. Since this application can achieve the deposition of single-layer molecules, that is, it can achieve film thickness control at the molecular level. It can be understood that after a single film layer is formed and stabilized, continuing to introduce monomers will not cause a reaction, that is, it will not increase the thickness of the previously obtained film layer. Therefore, the method of this application can effectively control the thickness of the thin film, and this deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers without double bonds, so as to adapt to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a thin film with a target thickness can be achieved.

[0049] Specifically, Figure 1 is a schematic flow chart of an initiation molecular layer deposition method provided by an embodiment of this application. Referring to Figure 1 , the initiation molecular layer deposition method includes the following steps:

[0050] (1) Surface activation: First, place the substrate in the reaction chamber, and then use plasma to treat the surface of the substrate to form reaction sites on the surface of the substrate. It should be noted that the reaction sites include free radicals and high-energy particles.

[0051] (2) Deposition: After reaction sites are formed on the surface of the substrate, introduce monomers into the reaction chamber. Under the action of the reaction sites, the monomers will deposit on the surface of the substrate to form a film layer. Among them, the monomers include the first type of monomers and the second type of monomers. The active groups of the first type of monomers include at least one double bond, and the second type of monomers include vinyl-free siloxane monomers and vinyl-free silazane monomers. Due to the limited reaction sites on the surface of the substrate and the limited time of introducing monomers, the monomers only react limitedly on the surface of the substrate and automatically stop reacting after a certain thickness of the film layer is generated, that is, self-limiting reaction.

[0052] In some embodiments, when the monomer is a first type of monomer (the active group includes at least one double bond), the monomer acts on the reaction site and deposits on the substrate surface to form a film layer, including: the first type of monomer connects to the reaction site and undergoes a self-polymerization reaction, depositing on the substrate surface to form a polymer film layer. Specifically, under the action of the reaction site, the active group of the polymerizable first type of monomer breaks open, one end of which connects to the reaction site on the substrate surface, and the other end undergoes a self-polymerization reaction and deposits on the substrate surface. 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, realizing the polymerization deposition of monomers containing double bonds.

[0053] In some embodiments, when the monomer is a second type of monomer (siloxane monomers without vinyl and silazane monomers without vinyl), the monomer acts on the reaction site and deposits on the substrate surface to form a film layer, including: the reaction site adsorbs the second type of monomer and deposits on the substrate surface to form a film layer. Specifically, the reaction site adsorbs the second type of monomer and deposits on the substrate surface by physical adsorption. When plasma treatment is performed again after the first film layer deposition, it will affect the structure of the first deposited film layer, that is, the film layer will transform into a corresponding inorganic oxide film layer or inorganic nitride film layer. At the same time, during the plasma treatment process, for example, the C-C bond of the monomer will break open and link with other monomers, thereby a polymer film layer can also be formed. Similarly, subsequent deposition cycles will affect the structure of the previously deposited film layer, and finally inorganic thin films and polymer thin films with the target thickness are obtained. Therefore, the method of the present application can not only prepare polymer thin films but also inorganic thin films.

[0054] (3) By sequentially and repeatedly performing the above surface activation and deposition steps, multiple film layers can be obtained, and the deposition of the film layer can be stopped according to actual needs to obtain a thin film with the target thickness.

[0055] The initiation-based molecular layer deposition method of the embodiments of the present application realizes high-precision control of the final film thickness by preparing the film layer multiple times, and is applicable to various polymerizable monomers containing double bonds and monomers without double bonds, with a simple process and high compatibility.

[0056] It should be noted that the initiation-based molecular layer deposition method of the embodiments of the present application can achieve precise control of the internal components of the thin film, that is, the components of each film layer in the thin film can be the same or different. Exemplarily, the first film layer in the thin film is polymerized from polymerizable monomer A, the second film layer is polymerized from polymerizable monomer B, the third film layer is polymerized from polymerizable monomer C, and the fourth film layer is polymerized from polymerizable monomer D. Of course, each polymer film layer in the thin film can also be polymerized from the same polymerizable monomer. In addition, the method of the present application can not only prepare polymer thin films with different polymer film layers but also prepare thin films composed of inorganic film layers and polymer film layers together.

[0057] It should be noted that after each surface activation step and each deposition step, a gas purge step can also be added to remove excess unreacted initiators, free radicals, by-products, etc.

[0058] In some embodiments, the thickness of the thin film is greater than or equal to 0.5 angstroms. Exemplarily, the thickness of the thin film can be 0.5 angstroms, 1 angstrom, 5 angstroms, 15 angstroms, 18 angstroms, 20 angstroms, 100 angstroms, 124 angstroms, 500 angstroms, 542 angstroms, 1000 angstroms, etc., and the specific values are not limited. The deposition method of the thin film in the embodiments of the present application realizes angstrom-level control of the thin film thickness, and the growth of a film layer with the same thickness can be achieved in each deposition cycle, which has certain technical advantages.

[0059] In some embodiments, the method for forming reaction sites 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.

[0060] Specifically, the reaction sites include free radicals and high-energy particles. The generation method of high-energy particles can include: generating high-energy particles on the surface of the substrate by plasma treatment of the substrate surface. These high-energy particles can adsorb monomers, thereby promoting the subsequent self-polymerization reaction of monomers or promoting the physical deposition process of monomers. The generation method of free radicals is: cracking the initiator by plasma treatment of the initiator to generate free radicals, and these free radicals can adsorb monomers and further initiate the self-polymerization reaction of monomers or promote the physical deposition process of monomers.

[0061] 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 compounds are one or more of azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN), or azodimethylformamide (ADMA). The peroxide compounds are one or more of di-tert-amyl peroxide (TAPO), di-tert-butyl peroxide ( tert TBPO), tert-butyl peroxybenzoate ( Tert TBPOB), or benzoyl peroxide (BPO). Tert -butyl peroxybenzoate, TBPOB) or benzoyl peroxide (BPO).

[0062] In some embodiments, the first type of monomers includes one or more of vinyl monomers containing a carbonyl group, styrene monomers, vinyl monomers containing an amide group, vinyl-containing siloxane monomers, and vinyl-containing silazane monomers. Among them, the vinyl monomers containing a carbonyl group are one or more of acrylic acid (AA), methyl methacrylate (MMA), glyceryl methacrylate (GMA), ethylene glycol diacrylate (EGDA), 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA), or 1H, 1H, 2H, 2H-perfluorodecyl acrylate (PFDA). The vinyl-containing siloxane monomers are one or more of 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane (V3D3), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4D4), or hexavinyldisiloxane (HVDSO). The vinyl-containing silazane monomers are one or more of 1,3,5-trivinyl-1,3,5-trimethylcyclotrisilazane (V3N3) or 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane (V4N4). The styrene monomers are one or more of styrene (S), divinylbenzene (DVB), pentafluorophenyl methacrylate (FM), or dimethylaminomethylstyrene (DMAMS).The ethylenic monomer with an amide is one or more of acrylamide (AAm), N,N - diethylacrylamide (DEAAm), or N,N - dimethylacrylamide (DMAAm). It shows that the deposition method of this application can achieve the polymerization deposition of various monomers with double bonds and has strong compatibility.

[0063] In a second aspect, the embodiments of this application provide a method for regulating regional selective deposition, including the following steps:

[0064] S201, Surface activation: Place the substrate in the reaction chamber and use plasma to form reaction sites on the substrate surface; wherein, the substrate includes 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;

[0065] S202, Deposition: Introduce monomers into the reaction chamber, and the monomers act on the reaction sites and deposit 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 vinyl - free siloxane monomers and vinyl - free silyl azide monomers;

[0066] S203, Etching: Etch and remove the film layer on the first surface;

[0067] S204, Repeat the surface activation, deposition, and etching steps in sequence until a thin film with a target thickness is obtained on the second surface.

[0068] This application uses plasma to first form reaction sites on the surface of a substrate with a first surface and a second surface of different materials, then allows monomers to act on the reaction sites and deposit a film layer on the substrate surface, and an etching process is added to achieve the effect of area-selective deposition of the thin film. During the process of forming reaction sites by plasma treatment, the amount of reaction sites formed each time can be controlled according to the plasma power, and then according to the time of introducing monomers, the thickness of the film layer deposited each time can be controlled, that is, self-limiting reaction. It should be noted that the film layer deposited each time can be a single-layer molecule or multiple-layer molecules, which depends on the time and amount of introducing monomers. After a single film layer is formed, the film layer is in a relatively stable state and its surface no longer has reaction activity. If it is necessary to continue depositing the film layer, it is necessary to use plasma to treat the surface of the previous film layer again to generate reaction sites, introduce monomers, and deposit the subsequent film layer to obtain a thin film with a target thickness. Since this application can achieve the deposition of single-layer molecules, that is, the film thickness can be controlled at the molecular level. It can be understood that after a single film layer is formed and stabilized, continuing to introduce monomers will not cause a reaction, that is, the thickness of the previous obtained film layer will not increase. Therefore, the method of this application can effectively control the thickness of the thin film, and this deposition method is applicable to a variety of polymerizable monomers including at least one double bond and monomers without double bonds, so as to adapt to the deposition of a variety of film layers. By controlling the number of cycles, the deposition of a thin film with a 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 show area selectivity. And 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 show area selectivity. Adding an etching step after each film layer deposition can remove the film layer on the first surface, thereby exposing the first surface again, and finally achieving the deposition of a thin film with a target thickness on the second surface of the substrate.

[0069] Specifically, Figure 2 is a schematic flow chart of a method for regulating area-selective deposition provided by an embodiment of this application, Figure 3 is a schematic diagram of the process of area-selective deposition of a thin film provided by an embodiment of this application. Refer to Figure 2 and Figure 3 , the method for regulating area-selective deposition of a thin film includes the following steps:

[0070] (1)Surface activation: First, place the substrate 1 in the reaction chamber, and then use plasma to treat the surface of the substrate 1 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 metal oxides with no variable valence.

[0071] (2)Deposition: After 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 will deposit on the surface of the substrate to form a film layer. Among them, 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 vinyl-free siloxane monomers and vinyl-free silazane monomers. Due to the limited reaction sites on the surface of the substrate 1 and the limited time for introducing the monomers, the monomers only undergo limited reactions on the surface of the substrate 1, and automatically stop reacting after a film layer 2 of a certain thickness is produced, that is, a self-limiting reaction.

[0072] In some embodiments, when the monomer is the first type of monomer (the active group includes at least one double bond), after the surface activation step and before the deposition step, the regioselective deposition control method further includes: introducing a co-oxidant into the reaction chamber to cause the first type of monomer to undergo a destructive reaction after the first type of monomer is introduced, so as 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 subsequent introduced first type of monomer first, resulting in the epoxidation of the vinyl group of the first type of monomer, causing the active groups that should participate in the self-polymerization reaction to be consumed, 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, thus resulting in regioselective deposition. In some embodiments, the co-oxidant includes one or more of peroxides, oxygen, ozone, and dinitrogen monoxide. Among them, the peroxides include di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl hydroperoxide, hydrogen peroxide, etc.

[0073] In some embodiments, when the monomer is the second type of monomer (vinyl-free siloxane monomers and vinyl-free silazane monomers), 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 (vinyl-free siloxane monomers and vinyl-free silazane monomers) 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 relatively high, and the deposition shows regioselectivity.

[0074] It should be noted that when the first type of monomers introduced are vinyl-containing siloxane monomers and vinyl-free silicon nitride monomers, since the monomers will also undergo ring-opening reactions, resulting in selectivity in deposition, the co-oxidant can also not be added.

[0075] (3) Etching: The film layer 2 on the surface of the substrate 1 is etched until all the film layer 2 on the first surface 11 is etched away. The 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 also exhibits regional selectivity. Removing the film layer 2 deposited on the first surface 11 can further expose the first surface 11, enabling the selective deposition effect to 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.

[0076] It should be further noted that when only the second type of monomers (vinyl-free siloxane monomers and vinyl-free silicon nitride monomers) are included, after the first film layer deposition and etching, when the plasma treatment is carried out again, it will affect the structure of the film layer deposited for the first time, that is, the film layer will be transformed into the corresponding oxide film layer or nitride film layer. At the same time, during the plasma treatment process, for example, the C-C bonds of the monomers will break and open, and link with other monomers, thereby a polymer film layer can also be formed. Similarly, the subsequent deposition cycles will affect the structure of the film layer deposited in the previous time, and finally inorganic thin films and polymer thin films with the target thickness are obtained. Therefore, the method of the present application can not only achieve the regional selective deposition of polymer thin films, but also achieve the regional selective deposition of oxide thin films and nitride thin films.

[0077] (4) By sequentially repeating the above surface activation, deposition, and etching steps, multiple film layers can be obtained, and the deposition of the film layer 2 can be stopped according to actual requirements to obtain a thin film with the target thickness.

[0078] The method for regulating the regional selective deposition of the thin film in the embodiment of the present application realizes the regional selective deposition of the thin film and the high-precision control of the thickness through multiple depositions of the film layer, and by using the first surface 11 and the second surface 12 with different materials and the etching step of the film layer 2. Moreover, it is applicable to various monomers (polymerizable monomers and monomers without double bonds), has a simple process and high compatibility, and can be widely applied in the fields of electronics, optoelectronics, biomedicine, etc.

[0079] It should be noted that the method for regulating the area-selective deposition of the thin film in the embodiments of the present application can achieve precise control of the internal components of the thin film, that is, the components of each layer of the thin film can be the same or different. Exemplarily, the first layer of the thin film is polymerized from the polymerizable monomer A, the second layer is polymerized from the polymerizable monomer B, the third layer is polymerized from the polymerizable monomer C, and the fourth layer is polymerized from the polymerizable monomer D. Of course, each polymer film layer in the thin film can also be polymerized from the same monomer. In addition, the method of the present application can not only achieve area-selective deposition of polymer thin films with different polymer film layers, but also achieve area-selective deposition of thin films composed of oxide film layers, nitride film layers and polymer film layers.

[0080] It should be added that after each surface activation, each deposition step and each etching step, a gas purge step can also be added to remove excess unreacted initiators, free radicals, by-products, etc. The thickness of the thin film, the method of forming reaction sites, the types of initiators and monomers are the same as the relevant parts of the first aspect, and will not be elaborated here.

[0081] Refer to Figure 3 , the deposition selectivity of the monomer on the second surface 12 is greater than 90%; the deposition selectivity c is: c = (b - a) / (b + a), where a represents the deposition thickness of the thin film on the first surface 11, and b represents the deposition thickness of the thin film on the second surface 12.

[0082] The method for regulating the area-selective deposition of the thin film in the embodiments of the present application further includes: in the formation process of at least one film layer, using one of the initiated chemical vapor deposition method, atomic layer deposition method, molecular layer deposition method or plasma-enhanced chemical vapor deposition method to replace the steps of surface activation and deposition to form the film layer.

[0083] As an exemplary illustration, in the formation process of the first film layer, the initiated molecular layer deposition method as in the first aspect is adopted. In the formation process of the second film layer, the initiated chemical vapor deposition method is adopted. In the formation process of the third film layer, the plasma-enhanced chemical vapor deposition method is adopted, and finally a thin film with a target thickness is obtained.

[0084] As another exemplary illustration, in the formation process of the first and second film layers, the initiated molecular layer deposition method as in 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. In the formation process of the fifth film layer, the molecular layer deposition method is adopted, and finally a thin film with a target thickness is obtained.

[0085] To further illustrate the present application, a method for initiated molecular layer deposition of a thin film and a method for regulating regioselective deposition provided by the present application will be described in detail below in conjunction with specific embodiments. Example 1

[0086] This example is a method for regulating regioselective deposition of a thin film, which specifically includes the following steps:

[0087] (1) Surface activation: Place the patterned substrate in the reaction chamber, activate the substrate surface with Ar plasma for 1 - 60 s to form active sites of high-energy particles, and then purge with Ar gas for 5 - 180 s; wherein, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0088] (2) Deposition: Introduce 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane (V 3 D 3 ) as a polymerizable monomer into the reaction chamber for 5 - 180 s to deposit a polymer film layer on the substrate surface, and then purge with Ar gas for 5 - 360 s.

[0089] (3) Repeat the surface activation and deposition steps 50 times in sequence until a thin film with a target thickness is obtained on the second surface, and this thin film is a SiOC(H) thin film.

[0090] In Example 1, the reaction chamber temperature is set to 10 - 100 °C, the substrate temperature is 0 - 80 °C, and the power of the plasma power supply is 5 - 500 W. In addition, use a heating jacket to heat the source bottle containing V 3 D 3 and keep it at 30 - 90 °C. Example 2

[0091] This example is a method for regulating regioselective deposition of a thin film, which specifically includes the following steps:

[0092] (1) Surface activation: Place the patterned substrate in the reaction chamber, introduce di-tert-butyl peroxide ( Tert -butylperoxide, TBPO) as an initiator and Ar plasma into the reaction chamber together for 1 - 60 s to generate free radicals on the substrate surface, and then purge with Ar gas for 5 - 180 s; wherein, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0093] (2) Deposition: 1,3,5 - trivinyl - 1,3,5 - trimethylcyclotrisiloxane (V 3 D 3 ) was introduced into the reaction chamber as a polymerizable monomer for 5 - 180 s to deposit a polymer film layer on the substrate surface, and then purged with Ar gas for 5 - 360 s.

[0094] (3) The surface activation and deposition steps were repeated 50 times in sequence until a thin film with a target thickness was obtained on the second surface, and this thin film was a SiOC(H) thin film.

[0095] In Example 2, the reaction chamber temperature was set at 10 - 100 °C, the substrate temperature was 0 - 80 °C, and the power of the plasma power supply was 5 - 500 W. In addition, the source bottles containing TBPO and V 3 D 3 were heated separately using heating jackets and maintained at 20 - 80 °C and 30 - 90 °C. During the preparation of the thin film in Example 2, at least one polymer film layer was prepared by initiated chemical vapor deposition method. Example 3

[0096] This example is a method for regulating the area - selective deposition of a thin film, specifically including the following steps:

[0097] (1) Surface activation: The patterned substrate was placed in the reaction chamber, and the surface of the substrate was activated with Ar plasma for 1 - 60 s to form active sites of high - energy particles, and then purged with Ar gas for 5 - 180 s; among them, the material of the first surface was Co, and the material of the second surface was SiO 2 .

[0098] (2) Deposition: 1,3,5 - trivinyl - 1,3,5 - trimethylcyclotrisiloxane (V 3 D 3 ) was introduced into the reaction chamber as a polymerizable monomer for 5 - 180 s to deposit a polymer film layer on the substrate surface, and then purged with Ar gas for 5 - 360 s.

[0099] (3) Etching: The polymer film layer was etched with O 2 and Ar for 5 - 40 s until the polymer film layer on the first surface was completely removed, and then purged with Ar gas for 5 - 180 s.

[0100] (4) The surface activation, deposition, and etching steps were repeated 50 times in sequence until a thin film with a target thickness was obtained on the second surface, and this thin film was a SiOC(H) thin film.

[0101] In Example 3, the reaction chamber temperature is set to 10 - 100 °C, the substrate temperature is 0 - 80 °C, and the power of the plasma power supply is 5 - 500 W. The flow rates of O 2 and Ar during the etching process are 1 - 50 sccm and 1 - 20 sccm respectively. In addition, a heating jacket is used to heat the source bottle containing V 3 D 3 and keep it at 30 - 90 °C. Example 4

[0102] This example is a method for regulating the area - selective deposition of a thin film, which specifically includes the following steps:

[0103] (1) Surface activation: Place the patterned substrate in the reaction chamber, introduce di - tert - butyl peroxide (TBPO) as an initiator and Ar plasma into the reaction chamber together for 1 - 60 s to generate free radicals on the substrate surface, and then purge with Ar gas for 5 - 180 s; wherein, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0104] (2) Deposition: Introduce 1,3,5 - trivinyl - 1,3,5 - trimethylcyclotrisiloxane (V 3 D 3 ) as a polymerizable monomer into the reaction chamber for 5 - 180 s to deposit a polymer film layer on the substrate surface, and then purge with Ar gas for 5 - 360 s.

[0105] (3) Etching: Use O 2 and Ar to perform plasma etching on the polymer film layer for 5 - 40 s until the polymer film layer on the first surface is completely removed, and then purge with Ar gas for 5 - 180 s.

[0106] (4) Repeat the surface activation, deposition, and etching steps 90 times in sequence until a thin film with a target thickness is obtained on the second surface, and this thin film is a SiOC(H) thin film.

[0107] In Example 4, the reaction chamber temperature is set to 10 - 100 °C, the substrate temperature is 0 - 80 °C, and the power of the plasma power supply is 5 - 500 W. The flow rates of O 2 and Ar during the etching process are 1 - 50 sccm and 1 - 20 sccm respectively. In addition, use a heating jacket to heat the source bottles containing TBPO and V 3 D 3 and keep them at 20 - 80 °C and 30 - 90 °C respectively.

[0108] Examples 5 - 13

[0109] Examples 5 - 13 are respectively a method for regulating the area - selective deposition of a thin film. The steps of Examples 5 - 13 are the same as those of Example 4, and the detailed information such as the substances used in each specific step is shown in Table 1.

[0110] Comparative Example 1

[0111] This comparative example is a method for regulating the area - selective deposition of a thin film, which specifically includes the following steps: Place the patterned substrate in the reaction chamber, introduce p - xylene monomer (a monomer without double bonds) into the reaction chamber for 1 - 60 s, and at the same time, use the Ar plasma initiation method to initiate the TBPO initiator to generate free radicals on the substrate surface, so as to deposit and form a polymer thin film on the substrate surface. Among them, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0112] Comparative Example 2

[0113] This comparative example is a method for regulating the area - selective deposition of a thin film, which specifically includes the following steps: Place the patterned substrate in the reaction chamber, introduce the TBPO initiator and toluene monomer (a monomer without double bonds) into the reaction chamber simultaneously for 1 - 60 s, and at the same time, use the thermal initiation method to initiate the TBPO initiator to generate free radicals on the substrate surface, so as to deposit and form a polymer thin film on the substrate surface. Among them, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0114] Comparative Example 3

[0115] This comparative example is a method for regulating the area - selective deposition of a thin film, which specifically includes the following steps: Place the patterned substrate in the reaction chamber, introduce the TBPO initiator and p - xylene monomer (a monomer without double bonds) into the reaction chamber simultaneously for 1 - 60 s, and at the same time, use the photo - initiation method to initiate the TBPO initiator to generate free radicals on the substrate surface, so as to deposit and form a polymer thin film on the substrate surface. Among them, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0116] Comparative Example 4

[0117] This comparative example is a method for regulating the area - selective deposition of a thin film, which specifically includes the following steps: Place the patterned substrate in the reaction chamber, introduce the TBPO initiator into the reaction chamber for 1 - 60 s, use the thermal initiation method to initiate the TBPO initiator to generate free radicals on the substrate surface, and then introduce propane monomer (a monomer without double bonds) to deposit and form a polymer film layer on the substrate surface. Repeat the above steps to form a polymer thin film. Among them, the material of the first surface is Co, and the material of the second surface is SiO 2 .

[0118] Table 1

[0119]

[0120] As can be seen from Table 1, compared with Comparative Examples 1-4, the deposition thickness of the thin film on the second surface in the embodiments of the present application is significantly greater than that on the first surface, indicating that the region-selective deposition control method in the embodiments of the present application can achieve selective deposition of the thin film on the second surface.

[0121] For the above-mentioned Embodiments 1-13, an ellipsometer was used to detect the thin film increment on the first surface and the second surface respectively, and the test results are listed in Table 1. Since an etching step was added during the deposition of the film layer in Embodiments 3-13, the deposition selectivity on the second surface is higher than 90%.

[0122] It should be noted that in this embodiment, a circulating water device was also used to control the substrate temperature of the reaction chamber and the temperature at the bottom of the quartz crystal microbalance, so that the two temperatures are kept consistent. During the deposition of the thin film in the same batch, two quartz crystal microbalances were used simultaneously to detect the thin film increment on the first surface and the second surface respectively. Figure 4 It is a schematic diagram of the mass change of the quartz crystal microbalance during the region-selective deposition of the thin film provided by the embodiment of the present application. As Figure 4 shown, the mass gap between the thin films on the first surface and the second surface gradually widens with the increase of the deposition cycle number, indicating that the region-selective deposition method of the thin film in the embodiments of the present application can improve the deposition selectivity.

[0123] Figure 5 It is an SEM image after the region-selective deposition of the thin film provided by the embodiment of the present application. Figure 6 It is a three-dimensional AFM image and a two-dimensional image after the region-selective deposition of the thin film with a strip-shaped structure on the first surface provided by the embodiment of the present application. Among them, the dark area is the area of the strip-shaped first surface, and the light area is the area of the second surface. Figure 7 It is a two-dimensional AFM image after the region-selective deposition of the thin film with a circular structure on the first surface provided by the embodiment of the present application and a height schematic diagram of the first surface and the second surface after deposition. Among them, the dark area in the left figure is the area of the circular first surface, and the light area is the area of the second surface. After the region-selective deposition in the right figure, the heights of the first surface and the second surface obtained according to the white line area in the left figure, that is, the heights of the thin film growth area and the non-growth area.

[0124] In order to demonstrate the effect of the region-selective deposition method of the thin film proposed in the embodiments of the present application, the deposition was carried out on a patterned substrate prepared by methods such as photolithography, evaporation, or magnetron sputtering, and the deposited substrate was characterized by SEM. As Figure 5 shown, whereFigure 5 In (a) shows the topographic map of the patterned substrate, Figure 5 In (b) shows the partial topographic map of the patterned substrate. The material of the first surface of the substrate is Co, and the material of the second surface is SiOC. After the selective deposition of the thin film region, the deposition thickness of the thin film on the first surface is 7.1 nm, and the deposition thickness on the second surface is 13.8 nm. This shows that the selective deposition method of the thin film region in the embodiment of the present application can improve the deposition selectivity.

[0125] As Figure 6 and Figure 7 shown, the substrate after the selective deposition of the thin film region in the embodiment of the present application is characterized by AFM. It can be seen from the figure that obvious region-selective deposition effects are presented on the first surface and the second surface of the substrate, indicating that the selective deposition method of the thin film region in the embodiment of the application can improve the deposition selectivity.

[0126] 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 equivalent technologies, the present application is also intended to include these changes and modifications.

Claims

1. A method for regulating and controlling 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 etching rate of the first surface is greater than the etching rate of the second surface; The surface activation, deposition and etching steps are repeated in sequence until a polymer film or an inorganic film with a target thickness is obtained on the second surface.

2. The method for regulating and controlling regional selective 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 film layer.

3. The method for regulating and controlling regional selective 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 regulating and controlling regional selective 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 regulating and controlling regional selective 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 regulating and controlling regional selective 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 regulating and controlling regional selective 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. The method for regulating and controlling regional selective deposition according to claim 1, 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.

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