Precursor for depositing metal-containing film as well as preparation method and application of precursor

Abstract

The invention provides a precursor for depositing a metal-containing film as well as a preparation method and application thereof, the precursor comprises a compound with a structure as shown in a formula I, R1, R2 and R3 are independently selected from one of H, C1-C6 linear alkyl, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C1-C6 alkoxy and halogen; r < 4 > and R < 5 > are respectively and independently selected from one of straight chain alkyl of C < 1-6 >, branched chain alkyl of C < 3-6 >, cyclic alkyl of C < 3-6 >, alkoxy of C < 1-6 > and halogen; r < 6 > to R < 10 > are independently selected from one of H, straight chain alkyl of C < 1 > to C < 6 >, branched chain alkyl of C < 3 > to C < 6 >, cyclic alkyl of C < 3 > to C < 6 > and alkoxy of C < 1 > to C < 6 >; n is 1, 2 or 3, and M is a metal element. The precursor provided by the invention can solve the problem of insufficient thermal stability of the existing alkylamine precursor.

Description

Technical Field

[0001] The present application belongs to the field of thin film deposition, and specifically relates to a precursor for depositing a metal-containing film, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of semiconductor technology, device fabrication processes and techniques have also evolved. Metal-containing thin films are increasingly being used, such as high-κ dielectric oxides for dynamic random access memory (DRAM) and ferroelectric perovskites for infrared detectors and non-volatile ferroelectric random access memory (NV-FeRAM). The fabrication techniques for these metal films have also been continuously improved. Chemical vapor deposition (CVD) offers many advantages over traditional techniques, while atomic layer deposition (ALD) offers even greater advantages in some areas.

[0003] In CVD / ALD processes, the properties of the precursor are crucial. At room temperature, the precursor must be highly stable for ease of production, transportation, and storage; it must also be highly volatile to facilitate its transport into the deposition chamber with the carrier gas. Furthermore, ALD precursors must maintain high thermal stability even at elevated temperatures (deposition temperatures) to prevent thermal decomposition.

[0004] Existing metal-containing alkyl amide precursors generally have high volatility and surface reactivity, but their thermal stability is insufficient. They decompose to a certain extent during the process of being transported from the storage container to the reactor, which limits their application. Summary of the Invention

[0005] The present application discloses a precursor for depositing a metal-containing film, which is used to solve the problem of insufficient thermal stability of existing alkyl amide precursors.

[0006] In a first aspect, the present application provides a precursor for depositing a metal-containing film, wherein the precursor comprises a compound having a structure shown in Formula I:

[0007]

[0008] Among them, R 1 、R 2 、R 3 Each is independently selected from H, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a halogen; R 4 、R 5Each is independently selected from a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a halogen; R 6 to R 10 Each is independently selected from one of H, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, and a substituted or unsubstituted C1-C6 alkoxy group; n is 1, 2 or 3, and M is a metal element.

[0009] The precursor of the embodiment of the present application includes a compound of the structure shown in Formula I, wherein the metal center M of the compound of the structure shown in Formula I is coordinated by different ligands, which are substituted or unsubstituted cyclopentadienyl (Cp), amidino (R 1 NC(R 2 )=NR 3 ), optionally an amino group (NR 4 R 5 ), this type of new heteroleptic metal compound has higher thermal stability, good saturated vapor pressure and adjustable reactivity than traditional metal-containing alkyl amide precursors, making it suitable for a higher atomic layer deposition (ALD) process temperature window when preparing metal-containing films, while ensuring the uniformity of the metal-containing films.

[0010] In one possible implementation, the M is a Group IVB metal element.

[0011] Among them, films containing Group IVB metals have good corrosion resistance, high-temperature stability, mechanical strength, biocompatibility, and excellent electrical and optical properties. When M is a Group IVB metal, the thin films prepared from the precursors have broader application prospects in many fields such as industry, electronics, medicine, and scientific research.

[0012] In one possible implementation, M is zirconium (Zr) or hafnium (Hf).

[0013] In the embodiment described above, the precursor in which M is Zr or Hf can be used to prepare a metal-containing film with a moderate dielectric constant and good thermal stability, which is compatible with traditional silicon-based integrated circuit processes and can be widely used in the manufacture of dynamic random access memory.

[0014] In one possible embodiment, the R 1 、R 2 、R 3 Each is independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;

[0015] and / or, the R 4 、R 5 Each is independently selected from methyl, ethyl, n-propyl, and isopropyl.

[0016] The compound with the structure described above can, on the one hand, improve the reactivity of the precursor through the electron-donating or electron-withdrawing effect of the substituents contained therein; on the other hand, due to the appropriate size of the substituents, it can not only ensure the good volatility of the precursor and help to achieve uniform transport and distribution during the vapor deposition process, but also further improve the stability of the precursor, reduce unnecessary decomposition or polymerization reactions of the precursor during storage and use, thereby further improving the purity of the metal-containing film.

[0017] In a second aspect, the present application provides a method for preparing the above-mentioned precursor, the preparation method comprising at least one of steps (1) to (3):

[0018] (1) reacting a compound having a structure represented by Formula II with a compound having a structure represented by Formula III to obtain the precursor;

[0019] (2) The compound having the structure shown in Formula IV reacts with the compound having the structure shown in Formula V to obtain intermediate 1, which reacts with M"(NR 4 R 5 ) undergoing a second reaction to obtain the precursor;

[0020] (3) The compound having the structure shown in Formula IV and M"(NR 4 R 5 ) undergoes a third reaction to obtain intermediate 2, and intermediate 2 undergoes a fourth reaction with the compound represented by formula V to obtain the precursor;

[0021] wherein M' and M" are independently selected from lithium, sodium or potassium.

[0022]

[0023] The preparation method of the above-mentioned precursor has a short preparation process, a simple synthesis method, low-cost and easily available raw materials, a high synthesis yield, and is suitable for industrial application.

[0024] In one possible embodiment, the molar ratio of the compound having the structure represented by Formula II to the compound having the structure represented by Formula III is 1:n;

[0025] And / or, the molar ratio of the compound having the structure shown in Formula IV to the compound having the structure shown in Formula V is 1:n; the intermediate 1 and the M"(NR 4 R 5 ) is a compound having a molar ratio of 1:3-n;

[0026] And / or, the compound having the structure shown in formula IV and the M"(NR 4 R 5 ) is 1:3-n; the molar ratio of the intermediate 2 to the compound of the structure represented by formula V is 1:n.

[0027] The above-described embodiment can further improve the yield and purity of the compound having the structure shown in Formula I by controlling the composition ratio of the reaction raw materials.

[0028] In a third aspect, the present application provides a compound prepared using the precursor described in the first aspect or the precursor prepared by the preparation method described in the second aspect, wherein M is a Group IVB metal element.

[0029] Since the compound described above is prepared using the precursor described in the first aspect or the precursor prepared by the preparation method described in the second aspect, it has excellent thermal stability and is suitable for manufacturing high-refractive index optical coatings, anti-corrosion coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers and gate dielectric insulating films in field effect transistors (FETs), capacitor electrodes, gate electrodes, adhesive diffusion barriers and integrated circuits, etc.

[0030] In a fourth aspect, the present application provides a method for forming a metal-containing film on at least one surface of a substrate, comprising:

[0031] a. providing the substrate having at least one surface in a reaction vessel;

[0032] b. Using the precursor described in the first aspect or the precursor prepared by the preparation method described in the second aspect, forming the metal-containing film on at least one surface of the substrate by chemical vapor deposition or atomic layer deposition process.

[0033] The method described above forms a metal-containing film on at least one surface of the substrate using the precursor provided in the first aspect, so that the metal-containing film can have a precisely defined thickness and high step coverage, and improve the density and uniformity of the metal-containing film.

[0034] In a fifth aspect, the present application provides a metal-containing film prepared by the method described in the third aspect.

[0035] The metal-containing film as described above has the advantages of precisely defined thickness, high step coverage, good compactness and uniformity.

[0036] In a sixth aspect, the present application provides a semiconductor memory comprising the metal-containing film described in the fourth aspect.

[0037] Since the semiconductor memory includes the metal-containing film of the fourth aspect, it has good storage density and data retention capability. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0039] Figure 1 The precursor of Example 1 of the present application 1 H NMR test result diagram;

[0040] Figure 2 This is a graph showing the TG-DSC test results of the precursor of Example 1 of the present application;

[0041] Figure 3 The precursor of Example 2 of this application 1 H NMR test result diagram;

[0042] Figure 4 This is a graph showing the TG-DSC test results of the precursor of Example 2 of the present application;

[0043] Figure 5 The precursor of Example 4 of this application 1 H NMR test result diagram;

[0044] Figure 6 This is a graph showing the TG-DSC test results of the precursor of Example 4 of the present application;

[0045] Figure 7 The precursor of Example 5 of the present application 1 H NMR test result diagram;

[0046] Figure 8 This is a graph showing the TG-DSC test results of the precursor of Example 5 of the present application;

[0047] Figure 9 The precursor of Example 6 of this application 1 H NMR test result diagram;

[0048] Figure 10 This is a graph showing the TG-DSC test results of the precursor of Example 6 of the present application. DETAILED DESCRIPTION

[0049] To make the purpose, technical solutions, and advantages of the embodiments of this application more clear, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0050] Throughout this application, references to "one embodiment," "an example," or "an example" mean that a particular feature, structure, or characteristic described in connection with that embodiment, embodiment, or example is included in at least one embodiment of the present invention. Therefore, appearances of the phrases "one embodiment," "an embodiment," "an example," or "an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combinations and / or subcombinations in one or more embodiments or examples.

[0051] In this application, the term "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0052] In a first aspect, the present application provides a precursor for depositing a metal-containing film, wherein the precursor comprises a compound having a structure shown in Formula I:

[0053]

[0054] Among them, R 1 、R 2 、R 3 Each is independently selected from H, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a halogen; R 4 、R 5 Each is independently selected from a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a halogen; R 6 to R10 Each is independently selected from one of H, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, and a substituted or unsubstituted C1-C6 alkoxy group; n is 1, 2 or 3, and M is a metal element.

[0055] The precursor of the embodiment of the present application has high thermal stability due to the compound of the structure shown in Formula I, and is suitable for atomic layer deposition of metal-containing films. Specifically, the metal center M of the compound of the structure shown in Formula I is coordinated by different ligands, which are substituted or unsubstituted cyclopentadienyl (Cp), amidino (R 1 NC(R 2 )=NR 3 ), optionally alkylamino (NR 4 R 5 ), this type of new heteroleptic metal compound has higher thermal stability and good saturated vapor pressure than traditional diheteroleptic metal compounds, and its volatility and reactivity can meet general requirements, making it suitable for a higher atomic layer deposition (ALD) process temperature window when preparing metal-containing films, while ensuring the uniformity of the metal-containing films.

[0056] It should be noted that the term "alkyl" in this application refers to a saturated functional group containing carbon and hydrogen atoms. For example, linear alkyl groups include (but are not limited to) methyl, ethyl, propyl, butyl, and pentyl, branched alkyl groups include (but are not limited to) isopropyl, isobutyl, sec-butyl, and tert-butyl, and cyclic alkyl groups include (but are not limited to) cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "substituted" in this application refers to at least one hydrogen atom in the alkyl group being replaced by a heteroatom such as N, F, Cl, P, or Br. M in this application can be a variety of metals used in the field of depositing metal-containing films. A specific metal element can be selected based on its conductivity, corrosion resistance, mechanical strength, optical properties, and biocompatibility to meet the needs of a specific application, such as aluminum (Al), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zu), titanium (Ti), vanadium (V), manganese (Mn), tungsten (W), molybdenum (Mo), chromium (Cr), and gold (Au).

[0057] n being 2 or 3 can further improve the thermal stability of the compound. In a specific embodiment, when n is 2, the precursor has the following general formula I-1:

[0058]

[0059] In a specific embodiment, when n is 3, the precursor has the following general formula I-2:

[0060]

[0061] In a specific embodiment, the M is a Group IVB metal element.

[0062] The term "Group IVB metal" refers to chemical elements belonging to Group IVB of the periodic table, and may include, for example, zirconium, hafnium, or titanium. Specifically, thin films containing Group IVB metals exhibit excellent corrosion resistance, high-temperature stability, mechanical strength, biocompatibility, and superior electrical and optical properties. When M is a Group IVB metal, the thin films deposited from the precursor have broad application prospects in fields such as industry, electronics, healthcare, and scientific research.

[0063] In a specific embodiment, the M is zirconium or hafnium.

[0064] Among them, zirconium or hafnium-containing precursors can be used to prepare metal-containing films with moderate dielectric constants and good thermal stability, which are compatible with traditional silicon-based integrated circuit processes and can be widely used in the manufacture of dynamic random access memories.

[0065] In a specific embodiment, the R 1 、R 2 、R 3 Each is independently selected from H, a substituted or unsubstituted C1-C4 linear alkyl group, a branched alkyl group, a cyclic alkyl group, or an alkoxy group;

[0066] and / or, the R 4 、R 5 Each is independently selected from H, a substituted or unsubstituted C1-C4 linear alkyl group, a branched alkyl group, a cyclic alkyl group, or an alkoxy group;

[0067] and / or, the R 6 to R 10 Each is independently selected from H, a substituted or unsubstituted C1-C4 linear alkyl group, a branched alkyl group, a cyclic alkyl group, or an alkoxy group.

[0068] In the embodiment described above, by further limiting the structure of the substituted R group, the molecular weight of the precursor can be controlled within a certain range, which helps to make the precursor easier to evaporate and transport to the reaction area during the deposition process, thereby improving the deposition rate and uniformity of the precursor, especially in chemical vapor deposition (CVD) and atomic layer deposition (ALD).

[0069] In a specific embodiment, the R 1 、R 2 、R 3Each is independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;

[0070] and / or, the R 4 、R 5 Each is independently selected from methyl, ethyl, n-propyl, and isopropyl.

[0071] Compounds with the structure described above can, on the one hand, improve the reactivity of the precursor through the electron donation or absorption effect of the substituents contained therein; on the other hand, due to the appropriate size and position of the substituents, not only can the good volatility of the precursor be ensured, which helps to achieve uniform transport and distribution during the vapor deposition process, but also the stability of the precursor can be further improved, thereby reducing unnecessary decomposition or polymerization reactions of the precursor during storage and use, thereby improving the purity of the metal-containing film.

[0072] In a specific embodiment, the precursor comprises at least one compound of the structure shown in Formula 1-53:

[0073]

[0074]

[0075]

[0076] In the above molecular structure, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, n = normal, i = iso, s = secondary.

[0077] In a second aspect, the present application provides a method for preparing the above-mentioned precursor, the preparation method comprising at least one of steps (1) to (3):

[0078] (1) reacting a compound having a structure represented by Formula II with a compound having a structure represented by Formula III to obtain the precursor;

[0079] (2) The compound having the structure shown in Formula IV reacts with the compound having the structure shown in Formula V to obtain intermediate 1, which reacts with M"(NR 4 R 5 ) undergoing a second reaction to obtain the precursor;

[0080] (3) The compound having the structure shown in Formula IV and M"(NR 4 R 5 ) undergoes a third reaction to obtain intermediate 2, and intermediate 2 undergoes a fourth reaction with the compound represented by formula V to obtain the precursor;

[0081] wherein M' and M" are independently selected from lithium, sodium or potassium;

[0082]

[0083] It can be understood that each of the above steps is a preparation method, that is, the preparation method of the precursor includes three methods. In detail, in step (1), the compound having the structure shown in formula II reacts with the compound having the structure shown in formula III. As an example but not a limitation, the reaction can be carried out in an organic solvent for 8 to 24 hours. The organic solvent is a liquid that can disperse the compound having the structure shown in formula II and the compound having the structure shown in formula III and does not react with the compound having the structure shown in formula II and the compound having the structure shown in formula III; the reaction is preferably carried out in an inert atmosphere. In step (2), the compound having the structure shown in formula IV reacts with the compound having the structure shown in formula V to obtain intermediate 1, which reacts with M"(NR 4 R 5 ) undergoes a second reaction to obtain the precursor; as an example but not a limitation, the above first reaction and second reaction can be carried out in an organic solvent, the time of the first reaction and the second reaction is 8 to 24 hours, and the organic solvent is a liquid that can disperse the raw material compound and does not react with the raw material compound; the first reaction and the second reaction are preferably carried out in an inert atmosphere. In step (3), the compound having the structure shown in formula IV is reacted with M"(NR 4 R 5 ) undergoes a fourth reaction to obtain intermediate 2, and intermediate 2 undergoes a fifth reaction with the compound of the structure shown in formula V to obtain the precursor. As an example and not a limitation, the above third reaction and fourth reaction can be carried out in an organic solvent, and the time for the third reaction and the fourth reaction is 8 to 24 hours. The organic solvent is a liquid that can disperse the raw material compound and does not react with the raw material compound; the third reaction and the fourth reaction are preferably carried out in an inert atmosphere.

[0084] As an example but not limitation, the organic solvent in steps (1) to (3) above can be one or a combination of hydrocarbon solvents and ether solvents, including (but not limited to) n-hexane, cyclohexane, petroleum ether, toluene, tetrahydrofuran, etc.

[0085] Since the composition ratio of the reaction raw materials affects not only the yield and purity of the product, but also the value of n in the molecular structure, in order to improve the yield and purity of the compound having the structure shown in Formula I, in a specific embodiment, the molar ratio of the compound having the structure shown in Formula II to the compound having the structure shown in Formula III is 1:n;

[0086] And / or, the molar ratio of the compound having the structure shown in Formula IV to the compound having the structure shown in Formula V is 1:n; the intermediate 1 and the M"(NR 4 R 5a molar ratio of 1:3-n of the compound having the structure of Formula II to the compound having the structure of Formula III;

[0087] and / or, a molar ratio of 1:3-n of the compound having the structure of Formula IV to the compound having the structure of Formula V; 4 R 5 a molar ratio of 1:3-n of the compound having the structure of Formula II to the compound having the structure of Formula III; and a molar ratio of 1:n of the intermediate 2 to the compound having the structure of Formula V.

[0088] The reaction temperature of each step above can be adjusted according to the extent of the reaction and the yield of the product.

[0089] In order to further improve the yield of the precursor, in a specific embodiment, in step (1), the temperature of the reaction is -78°C to 50°C.

[0090] In step (2), the temperature of the first reaction is -78°C to 30°C, and the temperature of the second reaction is -78°C to 50°C.

[0091] In step (3), the temperature of the third reaction is -78°C to 30°C, and the temperature of the fourth reaction is -78°C to 50°C.

[0092] The precursor of the present application can be used to form a metal-containing film and can employ various deposition techniques, including but not limited to reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD), and atomic layer deposition (ALD) in the embodiments of the present application.

[0093] In a third aspect, the present application provides a compound prepared using the precursor of the first aspect or the precursor prepared by the preparation method of the second aspect, wherein M is a Group IVB metal element.

[0094] The compound as described above, which is prepared using the precursor of the first aspect or the precursor prepared by the preparation method of the second aspect, has excellent thermal stability and is suitable for use as a high-refractive-index optical coating, a corrosion-resistant coating, a photocatalytic self-cleaning glass coating, a biocompatible coating, a dielectric capacitor layer and a gate dielectric insulating film in a field effect transistor (FET), a capacitor electrode, a gate electrode, an adhesive diffusion barrier, and an integrated circuit, etc. in nanotechnology and the manufacture of semiconductor devices.

[0095] In a fourth aspect, the present application provides a method for forming a metal-containing film on at least one surface of a substrate, comprising:

[0096] a. providing the substrate having the at least one surface in a reaction vessel;

[0097] b. Using the precursor described in the first aspect or the precursor prepared by the preparation method described in the second aspect, forming the metal-containing film on at least one surface of the substrate by chemical vapor deposition or atomic layer deposition process.

[0098] The method described above uses the precursor provided by the first aspect to form a metal-containing film on at least one surface of the substrate through a chemical vapor deposition or atomic layer deposition (ALD) process, so that the metal-containing film can have a precisely defined thickness and high step coverage, and improve the density and uniformity of the metal-containing film.

[0099] By way of example and not limitation, in some embodiments of the present application, the atomic layer deposition process includes, but is not limited to, the following process: (i) sequentially introducing reactants including precursors and reactive gases into a reactor such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; and (ii) exposing the substrate to the reactants including the precursors and reactive gases by moving or rotating the substrate to different sections of the reactor (i.e., a spatial ALD reactor or a roll-to-roll ALD reactor), wherein the sections are separated by an inert gas curtain. The reactive gases include (but are not limited to) water, ozone, ammonia, and the like.

[0100] By way of example and not limitation, in some embodiments of the present application, chemical vapor deposition includes but is not limited to the following processes: (i) a precursor gas is introduced into a reaction chamber and transported to the surface of a substrate via a carrier gas; (ii) the precursor gas undergoes a chemical reaction (thermal decomposition, oxidation-reduction, hydrogenation or other chemical reaction) on or near the surface of the substrate to generate a solid product which is deposited on the substrate, and the solid product generated by the reaction gradually grows on the surface of the substrate to form a uniform thin film; wherein the above-mentioned carrier gas (such as hydrogen, nitrogen or argon) is mixed to help transport and control the gas flow.

[0101] In a fifth aspect, the present application provides a metal-containing film prepared by the method described in the fourth aspect.

[0102] The metal-containing film as described above has the advantages of precisely defined thickness, high step coverage, good compactness and uniformity.

[0103] The present application does not specifically limit the application scenarios of the metal-containing film (especially the metal-containing thin film), such as in the manufacture of nanotechnology and semiconductor devices. Examples of such applications include high-refractive-index optical coatings, anti-corrosion coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers and gate dielectric insulating films in field-effect transistors (FETs), capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits.

[0104] By way of example and not limitation, in some embodiments of the present application, the metal-containing film is used in microelectronic applications, such as high-κ dielectric oxides for dynamic random access memory (DRAM) applications, ferroelectric perovskites for infrared detectors and non-volatile ferroelectric random access memory (NV-FeRAM), and the like.

[0105] In a sixth aspect, the present application provides a semiconductor memory comprising the metal-containing film described in the fourth aspect.

[0106] Since the semiconductor memory includes the metal-containing film of the fourth aspect, it has good storage density and data retention capability.

[0107] The following is a detailed introduction to the precursors of the embodiments of the present application through specific examples.

[0108] Example 1

[0109] This example provides a precursor, including a compound with the structure shown in Formula 39, and its preparation method is as follows:

[0110]

[0111] Under a nitrogen atmosphere, CpZr(NMe2)3 (8.50 g, 30.0 mmol) and 100 mL of THF were added to a Schlenk flask at room temperature. A THF solution (50 mL) of iBuNH-C(H)=NiBu (9.45 g, 60.5 mmol) was slowly added dropwise at -30°C over 30 minutes. The mixture was allowed to slowly return to room temperature and allowed to react for 24 hours. The solvent was removed under vacuum. Evaporation under reduced pressure afforded a light yellow liquid, 5.31 g (35% yield) of the compound represented by Formula 39.

[0112] Figure 1 The product prepared in this example 1 H NMR spectrum, 1 H NMR (C6D6) δ ppm = 7.54 (s, 2H), 6.27 (s, 5H), 3.19 (s, 6H), 2.82 (br, 8H), 1.75 (br, 4H), 0.89 (d, 24H).

[0113] Figure 2 This is the thermogravimetric analysis (TG) diagram of the product prepared in this example. The heating rate during the thermogravimetric analysis process is 10K / min. The temperature T1 / 2 when half of the product is vaporized during the heating period is 293.7°C. The mass of the residue left after complete vaporization is 7.18%, confirming that the compound has high thermal stability.

[0114] Example 2

[0115] This example provides a precursor, including a compound with a structure shown in Formula 40, and its preparation process is as follows:

[0116]

[0117] The specific steps differ from those in Example 1 in that iBuNH-C(H)=NiBu was replaced with iBuNH-C(Me)=NiBu (10.30 g, 60.5 mmol) and distilled under reduced pressure to obtain 5.45 g of a light yellow liquid (yield 34%).

[0118] Figure 3 The product prepared in this example 1 H NMR spectrum, 1 H NMR (C6D6) δ ppm = 6.22 (s, 5H), 3.16 (s, 6H), 2.89 (br, 8H), 1.74 (br, 4H), 1.52 (s, 6H), 0.90 (d, 24H).

[0119] Figure 4 This is the thermogravimetric analysis (TG) diagram of the product prepared in this example. The heating rate during the thermogravimetric analysis process is 10K / min. The mass change of the first step is -5.60%, the starting point of the mass loss of the second step is 266.7℃, the inflection point is 306.6℃, and the end point is 334.3℃. The temperature T1 / 2 when half of the product is vaporized during the thermogravimetric analysis is 299.6℃, and the mass of the residue left after complete vaporization is 6.4%, which confirms that the compound has high thermal stability.

[0120] Example 3

[0121] This example provides a precursor, including a compound with the structure shown in Formula 39, and its preparation method is as follows:

[0122]

[0123] Under an inert atmosphere, a 1-L Schlenk flask was charged with 300 mL of THF and iBuNH-C(H)=NiBu (9.45 g, 60.5 mmol) at room temperature and cooled to -78°C. A 2.5 mol / L n-butyllithium solution in n-hexane (24.2 mL, 60.5 mmol) was slowly added dropwise to the reaction system. After complete addition, the mixture was allowed to return to room temperature and allowed to react for 2 h. The system was then cooled to 0°C, and cyclopentadienylzirconium trichloride (7.73 g, 30 mmol) was slowly added via a solid-state injector. After returning to room temperature, the reaction was continued for 8 h. The reaction system was then cooled to 0°C, and lithium dimethylamine (1.53 g, 30 mmol) was slowly added via a solid-state injector. After returning to room temperature, the reaction was continued for 12 h. The solvent was removed under vacuum, and n-hexane was added. The mixture was filtered through a sand core, and the solvent was removed under vacuum. The residue was distilled under reduced pressure to yield 4.55 g of a pale yellow liquid (30% yield). 1 H NMR (C6D6) δ ppm = 7.54 (s, 2H), 6.27 (s, 5H), 3.19 (s, 6H), 2.82 (br, 8H), 1.75 (br, 4H), 0.89 (d, 24H).

[0124] Example 4

[0125] This example provides a precursor, including a compound with the structure shown in Formula 51,

[0126]

[0127] The preparation method is as follows:

[0128]

[0129] Under an inert atmosphere, CpZr(NMe2)3 (8.50 g, 30.0 mmol) and 100 mL of THF were added to a Schlenk flask at room temperature. A THF solution (50 mL) of sBuNH-C(Me)=NsBu (5.36 g, 31.5 mmol) was slowly added dropwise at -30°C over 30 minutes. The mixture was allowed to slowly return to room temperature and allowed to react for 24 hours. The solvent was removed under vacuum to yield a yellow viscous liquid. Evaporation under reduced pressure afforded 3.43 g of a light yellow liquid (28% yield).

[0130] Figure 5 The product prepared in this example 1 H NMR spectrum, 1 H NMR (C6D6) δ ppm = 6.19 (d, 5H), 3.04 (m, 2H), 2.96 (t, 12H), 1.49 (d, 3H), 1.36 (m, 4H), 1.03 (d, 6H), 0.84 (dt, 6H).

[0131] Figure 6 This is the thermogravimetric analysis (TG) diagram of the product prepared in this example. The heating rate during the thermogravimetric analysis process is 10K / min. The starting point of its mass loss is 222.8℃, the inflection point is 254.1℃, and the end point is 280.2℃. The temperature T1 / 2 when half of the product is vaporized during the thermogravimetric analysis is 270.0℃, and the mass of the residue left after complete vaporization is 15.3%, indicating that the compound has a certain thermal stability.

[0132] Example 5

[0133] This example provides a precursor, including a compound with the structure shown in Formula 52,

[0134]

[0135] The preparation method is as follows:

[0136]

[0137] The specific steps differ from those in Example 4 in that sBuNH-C(Me)=NsBu was replaced with sBuNH-C(Et)=NsBu (5.80 g, 31.5 mmol) and distilled under reduced pressure to obtain 4.06 g of a light yellow liquid (yield 32%).

[0138] Figure 7 The product prepared in this example 1 H NMR spectrum, 1 H NMR (C6D6) δ ppm = 6.19 (d, 5H), 3.04 (m, 2H), 2.96 (t, 12H), 1.49 (d, 3H), 1.36 (m, 4H), 1.03 (d, 6H), 0.84 (dt, 6H).

[0139] Figure 8 This is the thermogravimetric analysis (TG) diagram of the product prepared in this example. The heating rate during the thermogravimetric analysis was 10K / min. The temperature T1 / 2 when half of the product was vaporized during the thermogravimetric analysis was 278.9°C. The mass of the residue left after complete vaporization was 17.03%, indicating that the compound has a certain thermal stability.

[0140] Example 6

[0141] This example provides a precursor, including a compound with the structure shown in Formula 53,

[0142]

[0143] The preparation method is as follows:

[0144]

[0145] The specific steps differ from those in Example 4 in that sBuNH-C(Me)=NsBu was replaced with tBuNH-C(H)=NtBu (4.92 g, 31.5 mmol) and distilled under reduced pressure to obtain 4.50 g of a light yellow liquid (yield 38%).

[0146] Figure 9 The product prepared in this example 1 H NMR spectrum, 1 H NMR (C6D6) δppm=8.28 (s, 1H), 6.17 (s, 5H), 2.98 (s, 12H), 1.06 (s, 18H).

[0147] Figure 10 This is the thermogravimetric analysis (TG) diagram of the product prepared in this example. The heating rate during the thermogravimetric analysis was 10K / min. The temperature T1 / 2 when half of the product was vaporized during the thermogravimetric analysis was 246.6°C. The mass of the residue left after complete vaporization was 8.7%, indicating that the compound has a certain thermal stability.

[0148] The above preferred embodiments further illustrate the purpose, technical solutions and advantages of the present application in detail. It should be understood that the above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A precursor for depositing a metal-containing film, characterized in that The precursor includes a compound having a structure shown in Formula I: Among them, R 1 、R 2 、R 3 Each is independently selected from H, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a halogen; R 4 、R 5 Each is independently selected from a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a halogen; R 6 to R 10 Each is independently selected from one of H, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted C3-C6 cyclic alkyl group, and a substituted or unsubstituted C1-C6 alkoxy group; n is 1, 2 or 3, and M is a metal element.

2. The precursor according to claim 1, characterized in that The M is a Group IVB metal element.

3. The precursor according to claim 2, characterized in that The M is zirconium or hafnium.

4. The precursor according to any one of claims 1 to 3, characterized in that The R 1 、R 2 、R 3 Each is independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; and / or, the R 4 、R 5 Each is independently selected from methyl, ethyl, n-propyl, and isopropyl.

5. A method for preparing the precursor according to any one of claims 1 to 4, characterized in that: The preparation method comprises at least one of steps (1) to (3): (1) reacting a compound having a structure represented by Formula II with a compound having a structure represented by Formula III to obtain the precursor; (2) The compound having the structure shown in Formula IV reacts with the compound having the structure shown in Formula V to obtain intermediate 1, which reacts with M"(NR 4 R 5 ) undergoing a second reaction to obtain the precursor; (3) The compound having the structure shown in Formula IV and M"(NR 4 R 5 ) undergoes a third reaction to obtain intermediate 2, and intermediate 2 undergoes a fourth reaction with the compound represented by formula V to obtain the precursor; wherein M' and M" are independently selected from lithium, sodium or potassium; 6. The preparation method according to claim 5, characterized in that The molar ratio of the compound having the structure represented by Formula II to the compound having the structure represented by Formula III is 1:n; And / or, the molar ratio of the compound having the structure shown in Formula IV to the compound having the structure shown in Formula V is 1:n; the intermediate 1 and the M"(NR 4 R 5 ) the molar ratio of the compound is 1:3-n; And / or, the compound having the structure shown in formula IV and the M"(NR 4 R 5 ) is 1:3-n; the molar ratio of the intermediate 2 to the compound of the structure represented by formula V is 1:n.

7. A compound, characterized in that The method is prepared using the precursor according to any one of claims 1 to 4 or the precursor prepared by the preparation method according to any one of claims 5 to 6, wherein M is a Group IVB metal element.

8. A method for forming a metal-containing film on at least one surface of a substrate, characterized in that include: a. providing the substrate having at least one surface in a reaction vessel; b. Using the precursor according to any one of claims 1 to 4 or the precursor prepared by the preparation method according to any one of claims 5 to 6, the metal-containing film is formed on at least one surface of the substrate by chemical vapor deposition or atomic layer deposition.

9. A metal-containing film, characterized in that Prepared by the method described in claim 8.

10. A semiconductor memory, characterized in that: Comprising the metal-containing film according to claim 9.

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