WO2024230100A1 - 金属互连结构的制备方法、金属互连结构及半导体组件 - Google Patents

金属互连结构的制备方法、金属互连结构及半导体组件 Download PDF

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WO2024230100A1
WO2024230100A1 PCT/CN2023/129331 CN2023129331W WO2024230100A1 WO 2024230100 A1 WO2024230100 A1 WO 2024230100A1 CN 2023129331 W CN2023129331 W CN 2023129331W WO 2024230100 A1 WO2024230100 A1 WO 2024230100A1
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layer
cobalt
metal
metal interconnect
preparing
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French (fr)
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栾庆洁
项金娟
袁鹏
焦正赢
王桂磊
赵超
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Beijing Superstring Academy of Memory Technology
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Beijing Superstring Academy of Memory Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/01—Manufacture or treatment
    • H10W20/071—Manufacture or treatment of dielectric parts thereof
    • H10W20/074—Manufacture or treatment of dielectric parts thereof of dielectric parts comprising thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
    • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
    • H10W70/611—Insulating or insulated package substrates; Interposers; Redistribution layers for connecting multiple chips together
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
    • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
    • H10W70/62—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their interconnections
    • H10W70/65—Shapes or dispositions of interconnections

Definitions

  • the present disclosure relates to the field of metal interconnection technology, and in particular to a method for preparing a metal interconnection structure, a metal interconnection structure and a semiconductor component.
  • Metal interconnection structure is a common structure in semiconductor devices.
  • Metal interconnection structure usually includes dielectric layer and interconnection wires separated by dielectric layer. Interconnection wires are usually used to realize electrical connection between multiple devices.
  • the material of interconnection wires is usually metal, such as copper. Metal atoms easily diffuse into dielectric layer, which may cause device failure. Therefore, metal interconnection structure usually introduces barrier layer between dielectric layer and interconnection wires.
  • a method for preparing a metal interconnect structure comprises the following steps:
  • a cobalt metal layer is prepared on the metal interconnect layer by atomic layer deposition using raw materials including cobalt organic compounds.
  • cobalt organic compounds cobalt atoms are bonded to four nitrogen atoms by single bonds, the four nitrogen atoms form pairs, and each pair of nitrogen atoms is connected by an organic group.
  • the cobalt organic compound has a structure as shown in general formula (1):
  • R 1 , R 2 , R 3 and R 4 are each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl;
  • L1 and L2 are each independently selected from substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C2-C20 alkenylene, substituted or unsubstituted C2-C20 alkynylene;
  • R5 is independently selected from alkyl, halogen, C1-C10 alkoxy, C1-C10 haloalkyl, C1-C10 haloalkoxy or C6-C20 aryl.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
  • L 1 and L 2 are each independently selected from methylene, 1,2-ethylene, 1,1-ethylene, 1,2-vinylene or ethynyl.
  • R 1 and R 2 are the same group.
  • R 3 and R 4 are the same group.
  • L 1 and L 2 are the same group.
  • the cobalt organic compound is selected from one of the following structures:
  • the raw material in the step of preparing the cobalt metal layer, further includes a reaction material capable of reacting with the cobalt organic compound, and the reaction material includes one or more of tert-butylamine and diethylamine.
  • the reaction temperature of the deposition process is controlled to be 100° C. to 400° C.
  • the process of depositing a cobalt metal layer includes one or more deposition cycles, each deposition cycle including introducing a cobalt organic compound, purging the cobalt organic compound, introducing a reaction material, and purging the reaction material, wherein the duration of introducing the cobalt organic compound is 1s to 30s, the duration of purging the cobalt organic compound is 1s to 30s, the duration of introducing the reaction material is 1s to 30s, and the duration of purging the reaction material is 1s to 30s.
  • the number of deposition cycles is controlled to be ⁇ 300.
  • the process of depositing the cobalt metal layer is performed in an atmosphere of a reducing gas.
  • the method after depositing the cobalt metal layer, the method further includes treating the cobalt metal layer with a reducing gas or plasma.
  • the material of the dielectric layer is selected from one or more of silicon dioxide, silicon-based polymer materials and carbon-doped silicon oxide.
  • the material of the metal interconnection layer is selected from one or more of platinum, cobalt, copper and ruthenium.
  • the method before preparing the metal interconnection layer in the interconnection groove, the method further includes:
  • a liner layer is prepared on the barrier layer, and the metal interconnection layer is prepared on the liner layer.
  • the present disclosure also provides a metal interconnection structure, which includes: a dielectric layer, a metal interconnection layer and a cobalt metal layer; the dielectric layer has an interconnection groove, the metal interconnection layer is located in the interconnection groove, the cobalt metal layer is arranged on the metal interconnection layer, and the cobalt metal layer is prepared on the metal interconnection layer by atomic layer deposition.
  • the raw material in the step of preparing the cobalt metal layer, further includes a reaction material capable of reacting with the cobalt organic compound, and the reaction material includes one or more of tert-butylamine and diethylamine.
  • the reaction temperature of the deposition process is controlled to be 100° C. to 400° C.
  • the thickness of the cobalt metal layer is ⁇ 30 nm, and the surface roughness of the cobalt metal layer is ⁇ 2 nm.
  • the proportion of cobalt atoms in the cobalt metal layer is ⁇ 90%.
  • the material of the dielectric layer is selected from one or more of silicon dioxide, silicon-based polymer materials and carbon-doped silicon oxide.
  • the material of the metal interconnection layer is selected from one or more of platinum, cobalt, copper and ruthenium.
  • the metal interconnect structure also includes a barrier layer, a pad layer and a metal seed layer arranged between the metal interconnect layer and the dielectric layer, and the barrier layer, the pad layer and the metal seed layer are stacked in sequence from the dielectric layer to the metal interconnect layer.
  • the present disclosure also provides a semiconductor component, which includes the metal interconnect structure as described in any of the above embodiments and a plurality of semiconductor devices, wherein the plurality of semiconductor devices are electrically connected through the metal interconnect structure.
  • the semiconductor component is a memory.
  • FIG1 is a schematic diagram of the steps of a method for preparing a metal interconnect structure disclosed in the present invention
  • FIG2 is a schematic diagram of the structure of a dielectric layer provided by the present disclosure.
  • FIG3 is a schematic diagram of a structure for preparing a barrier layer based on the structure shown in FIG2 ;
  • FIG4 is a schematic diagram of a structure for preparing a cushion layer based on the structure shown in FIG3 ;
  • FIG5 is a schematic diagram of a structure for preparing a metal seed layer and a metal interconnect layer based on the structure shown in FIG4 ;
  • FIG6 is a schematic diagram of a structure after planarization treatment is performed on the basis of the structure shown in FIG5 ;
  • FIG7 is a schematic diagram of a structure for preparing a cobalt metal layer based on the structure shown in FIG6 ;
  • the technical solutions described in an open manner may include open technical solutions that contain the listed technical features, or closed technical solutions composed of the listed features.
  • alkyl refers to a saturated hydrocarbon group containing primary (normal) carbon atoms, secondary carbon atoms, tertiary carbon atoms, quaternary carbon atoms or a combination thereof, with one bonding site.
  • Alkyl can be considered as a hydrocarbon group with one hydrogen atom less than the corresponding alkane and a corresponding bonding site. Phrases containing this term, such as "C1-C20 alkyl" means that the alkyl portion contains 1 to 20 carbon atoms.
  • Suitable examples include, but are not limited to, methyl (—CH 3 ), ethyl (—CH 2 CH 3 ), 1-propyl (n-propyl, —CH 2 CH 2 CH 3 ), 2-propyl (isopropyl, —CH(CH 3 ) 2 ), 1-butyl (n-butyl, —CH 2 CH 2 CH 2 CH 3 ), 2-methyl-1-propyl (—CH 2 CH(CH 3 ) 2 ), 2-butyl (—CH(CH 3 )CH 2 CH 3 ), 1,1-dimethylethyl (tert-butyl, —C(CH 3 ) 3 ), 1-pentyl (n-pentyl, —CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (—CH(CH 3 )CH 2 CH 2 CH 3 ), 3 - pentyl (—CH(CH 2 CH 3 ) 2 ), 2-methyl-2-butyl (—C(CH 3 ) 2CH2CH3 ), 3-
  • an alkylene group refers to a saturated hydrocarbon group having two bonding sites.
  • An alkylene group can be considered to be a hydrocarbon group in which two hydrogen atoms are removed from the corresponding alkane and two bonding sites are generated accordingly.
  • Phrases containing this term, such as "C1-C20 alkylene group” means that the alkylene portion contains 1 to 20 carbon atoms.
  • An alkylene group can be a group in which one hydrogen atom is removed from the above alkyl group and a bonding site is formed at the corresponding position. Suitable examples include, but are not limited to, methylene (-CH 2 -), ethylene (-CH(CH 3 )-), and 1,2-ethylene (-CH 2 CH 2 -).
  • alkenyl may also be referred to as olefin group, which refers to an unsaturated hydrocarbon group containing one or more carbon-carbon double bonds and one bonding site.
  • Alkenyl can be considered as a hydrocarbon group with one hydrogen atom missing from the corresponding olefin and a corresponding bonding site.
  • Terms containing this phrase, such as "C1-C20 alkenyl” means that the alkenyl part contains 1-20 carbon atoms.
  • alkenylene refers to an unsaturated hydrocarbon group having one or more carbon-carbon double bonds and two bonding sites.
  • Alkenylene can be considered as a hydrocarbon group with two hydrogen atoms missing from the corresponding olefin and correspondingly producing two bonding sites.
  • Phrases containing this term, such as "C1-C20 alkenylene” means that the alkenylene part contains 1 to 20 carbon atoms.
  • alkynyl may also be referred to as alkynyl, which refers to an unsaturated hydrocarbon group containing one or more carbon-carbon triple bonds and one bonding site.
  • Alkynyl can be considered as a hydrocarbon group with one hydrogen atom missing from the corresponding alkyne and a corresponding bonding site.
  • Terms containing this phrase, such as "C1-C20 alkynyl” means that the alkynyl part contains 1-20 carbon atoms.
  • Alkynyl can be a hydrocarbon group with four hydrogen atoms missing from the above alkyl group and a triple bond formed between two carbon atoms. Suitable examples include, but are not limited to, ethynyl (-C ⁇ CH) and propargyl ( -CH2C ⁇ CH ).
  • alkynylene refers to an unsaturated hydrocarbon group having one or more carbon-carbon triple bonds and two bonding sites.
  • Alkynylene can be considered as a hydrocarbon group with two hydrogen atoms missing from the corresponding alkyne and correspondingly two bonding sites.
  • Phrases containing this term, such as "C1-C20 alkynylene” means that the alkynylene part contains 1 to 20 carbon atoms.
  • Alkynylene can be a group that lacks one hydrogen atom on the basis of the above alkynyl and forms a bonding site at the corresponding position. Suitable examples include, but are not limited to: ethynylene (-C ⁇ C-) and propargylene (-CH 2 C ⁇ C-).
  • alkoxy refers to a group of an alkyl group connected to an oxygen atom, that is, a structure in which the alkyl group as defined above is connected to a parent core via an oxygen atom.
  • Hydroalkoxy refers to a structure in which the hydrogen atom of the alkyl part in the alkoxy group is replaced by a halogen atom.
  • halogen atom refers to F, Cl, Br or I.
  • the present disclosure provides a method for preparing a metal interconnect structure, which comprises the following steps:
  • a cobalt metal layer is prepared on a metal interconnect layer by atomic layer deposition using raw materials including cobalt organic compounds.
  • cobalt organic compounds cobalt atoms are bonded to four nitrogen atoms by single bonds, the four nitrogen atoms form pairs, and each pair of nitrogen atoms is connected by an organic group.
  • the metal interconnect structure refers to a structure that is connected to multiple devices at the same time and is used to achieve electrical conduction.
  • the metal interconnect structure generally includes a dielectric layer and a metal interconnect layer prepared in the dielectric layer.
  • the metal interconnect structure also includes a cobalt metal layer located on the metal interconnect layer, and a cobalt precursor can be used to prepare the cobalt metal layer.
  • cobalt metal layer For the preparation of cobalt metal layer, it is required that the cobalt metal layer can be selectively deposited only on the metal interconnect layer, and basically not deposited on the dielectric layer.
  • the traditional technology can only achieve selective preparation by chemical vapor deposition, and has not been able to achieve selective preparation of cobalt by atomic layer deposition.
  • problems such as poor controllability of chemical vapor deposition and poor quality of cobalt films have become increasingly prominent.
  • the material of the dielectric layer should be an insulating material, usually a non-metallic insulating material.
  • the cobalt organic compound having the above structure can be selectively adsorbed on substrates of different materials. Specifically, the cobalt organic compound can be selectively adsorbed on metal materials including copper, ruthenium and platinum, but is difficult to be adsorbed on On non-metallic dielectric materials including silicon, silicon dioxide and silicon nitride.
  • the preparation process of atomic layer deposition requires the precursor material to be adsorbed on the deposition substrate first. Therefore, using this type of cobalt organic compound as a precursor can make the cobalt film selectively formed on the metal interconnect layer, while the dielectric layer basically has no cobalt atoms or it is difficult to form a cobalt film.
  • a raw material including a cobalt organic compound is used to prepare a cobalt metal layer on the metal interconnect layer by atomic layer deposition.
  • the cobalt organic compound the cobalt atom is bonded to four nitrogen atoms by a single bond, and the four nitrogen atoms are paired in pairs, and each pair of nitrogen atoms is connected by an organic group.
  • the cobalt organic compound having the above structure can be used as a reaction raw material for the atomic layer deposition method, and during the atomic layer deposition process, the cobalt organic compound can be selectively adsorbed on the metal interconnect layer and basically not adsorbed on the dielectric layer, so that the formed cobalt film is also selectively formed on the metal interconnect layer.
  • preparing a cobalt film by atomic layer deposition can effectively improve the controllability of the preparation of the cobalt film and the quality of the film.
  • controllability of the preparation of the cobalt film may include parameters such as the minimum thickness of the cobalt film, the surface roughness, and the proportion of cobalt atoms in the cobalt metal layer.
  • the cobalt organic compound has a structure as shown in general formula (1):
  • R 1 , R 2 , R 3 and R 4 are each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl;
  • L1 and L2 are each independently selected from substituted or unsubstituted C1-C20 alkylene, substituted or unsubstituted C2-C20 alkenylene, substituted or unsubstituted C2-C20 alkynylene;
  • R5 is independently selected from alkyl, halogen, C1-C10 alkoxy, C1-C10 haloalkyl, C1-C10 haloalkoxy or C6-C20 aryl.
  • the cobalt atom is bonded to four nitrogen atoms by single bonds, and Furthermore, the four nitrogen atoms form pairs, and the two nitrogen atoms in a pair are connected by an organic chain segment, and each nitrogen atom may also be connected to a substituent.
  • R 1 , R 2 , R 3 and R 4 can be independently selected from C1-C10 alkyl, C2-C10 alkenyl or C2-C10 alkynyl. Further, R 1 , R 2 , R 3 and R 4 can be independently selected from C1-C5 alkyl, C2-C5 alkenyl or C2-C5 alkynyl. By selecting a group with a small number of carbon atoms, it is helpful to make the cobalt organic compound easier to gasify and adsorb onto the metal interconnect layer during the preparation process, thereby improving the uniformity and manufacturing efficiency of the cobalt metal layer.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from a C3-C4 alkyl group, such as a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group.
  • the structural formula of the n-propyl group is -CH 2 CH 2 CH 3
  • the structural formula of the isopropyl group is -CH(CH 3 ) 2
  • the structural formula of the n-butyl group is -CH 2 CH 2 CH 2 CH 3
  • the structural formula of the isobutyl group is -CH(CH 3 )CH 2 CH 3
  • the structural formula of the tert-butyl group is -C(CH 3 ) 3 .
  • L1 and L2 are each independently selected from C1-C10 alkylene, C2-C10 alkenylene or C2-C10 alkynylene.
  • R1 , R2 , R3 and R4 can each be independently selected from C1-C5 alkylene, C2-C5 alkenylene or C2-C5 alkynylene.
  • L1 and L2 are each independently selected from C1-C2 alkylene, C2 alkenylene and C2 alkynylene.
  • the cobalt precursor can have a higher reactivity and the reaction by-products can be removed more easily.
  • R 1 , R 2 , R 3 and R 4 are selected from the same group, for example, R 1 , R 2 , R 3 and R 4 are collectively isopropyl or tert-butyl.
  • L1 and L2 are also selected from the same group, for example, L1 and L2 can be 1,1-ethylene, 1,2-ethylene, 1,2-vinylene or ethynylene.
  • the general formula (1) is selected from one of the following structures:
  • the cobalt precursor shown in the above structural formula is particularly suitable for atomic layer deposition, which can be deposited on metal substrates such as platinum, copper and ruthenium to form a cobalt film with a cobalt atomic content of more than 90%, and on substrates such as silicon and silicon dioxide. No deposition occurs on the bottom.
  • the two pairs of nitrogen atoms and the connected segments can be conjugated and generate delocalized electron pairs, making the structure in the above formula more stable.
  • the preparation process of the metal interconnect structure includes the following steps:
  • a cobalt metal layer is prepared on the metal interconnect layer, and the step of preparing the cobalt metal layer comprises: using a raw material including the cobalt precursor to deposit the cobalt metal layer on the metal interconnect layer by an atomic layer deposition method.
  • the cobalt precursor provided by the present disclosure can be used as the cobalt raw material required for the atomic layer deposition method, and can be selectively deposited on the metal substrate instead of being deposited on the dielectric layer.
  • the cobalt precursor can be used to achieve layer-by-layer preparation of the cobalt metal layer by atomic layer deposition, improve the controllability of the cobalt metal layer in terms of film thickness and film uniformity, and is also conducive to obtaining a higher quality cobalt metal layer to meet the needs of smaller size devices.
  • the present disclosure also provides a schematic diagram of the steps of a method for preparing a metal interconnect structure as shown in Figure 1.
  • the method for preparing a metal interconnect structure includes steps S1 to S5.
  • Step S1 providing a dielectric layer.
  • Fig. 2 is a schematic diagram showing the structure of a dielectric layer 110 provided by the present disclosure.
  • the dielectric layer 110 is provided with interconnection grooves 111 .
  • the interconnection groove 111 is used to be filled with the subsequently prepared metal interconnection layer 150.
  • the interconnection groove 111 shown in FIG. 2 is in a multi-layered stepped shape, but in the actual preparation process, the interconnection groove 111 can also be prepared in other shapes, for example, the cross-section of the hole can be in a trapezoidal shape, a rectangular shape or an irregular shape, as long as the metal interconnection layer 150 can be filled and prepared.
  • the material of the dielectric layer 110 may be a low dielectric constant material (also referred to as a low-K material).
  • the dielectric constant of the material of the dielectric layer 110 is ⁇ 3.9.
  • the dielectric constant of the dielectric layer 110 is ⁇ 2.8.
  • the material of the dielectric layer 110 may include a silicon compound.
  • the material of the dielectric layer 110 may be selected from one or more of silicon dioxide, silicon-based polymer materials, carbon-doped silicon oxide, and silicon-based aerogel.
  • the silicon-based polymer material may be, for example, one or more of SiLK, HSQ (hydrogen silsesquioxane), and MSQ (methylsilsesquioxane).
  • the carbon-doped silicon oxide may be, for example, one or more of Black Diamond, Coral, and Aurora.
  • the material of the dielectric layer 110 includes silicon dioxide.
  • Step S2 preparing a barrier layer and a liner layer in the interconnection groove.
  • Fig. 3 is a schematic diagram showing a structure in which a barrier layer 120 is prepared based on the structure shown in Fig. 2. Referring to Fig. 3, the barrier layer 120 is prepared in the interconnection groove 111 and covers the groove wall of the interconnection groove 111.
  • the barrier layer 120 is used to separate the dielectric layer 110 and the subsequently prepared metal interconnection layer 150 , and to prevent metal atoms in the metal interconnection layer 150 from diffusing into the dielectric.
  • the material of barrier layer 120 may include one or more of tantalum, tantalum nitride, titanium, titanium nitride, and titanium silicon nitride. In this embodiment, the material of barrier layer 120 may include tantalum nitride.
  • the barrier layer 120 may also be a composite layer formed of multiple materials.
  • the barrier layer 120 may be a composite layer formed by stacking a tantalum layer and a tantalum nitride layer.
  • the method of preparing the barrier layer 120 may be a chemical vapor deposition method or an atomic layer deposition method.
  • the material of the barrier layer 120 may also be deposited on the surface of the dielectric layer 110 outside the interconnection groove 111 .
  • the thickness of the barrier layer 120 may be limited according to actual needs. In some examples of this embodiment, the thickness of the barrier layer 120 may be 0.5 nm to 10 nm. Further, the thickness of the barrier layer 120 may be 0.5 nm to 5 nm. Further, the thickness of the barrier layer 120 may be 0.5 nm to 3 nm.
  • Fig. 4 is a schematic diagram showing a structure of preparing a liner layer 130 based on the structure shown in Fig. 3. As shown in Fig. 4, the liner layer 130 is prepared in the interconnection groove 111 and is stacked on the surface of the barrier layer 120.
  • the liner layer 130 can also be used to separate the dielectric and the subsequently prepared metal interconnect layer 150.
  • the liner layer 130 can also serve as a nucleation substrate for the subsequently prepared seed layer to improve the uniformity and gap filling capability of the subsequently prepared layer.
  • the material of the liner layer 130 may be one or more of cobalt and ruthenium.
  • the method of preparing the liner layer 130 may be chemical vapor deposition or atomic layer deposition. Accumulation method.
  • the thickness of the liner layer 130 may be 1 nm to 10 nm. Further, the thickness of the liner layer 130 may be 1 nm to 5 nm. Further, the thickness of the liner layer 130 may be 1 nm to 3 nm.
  • the material of the liner layer 130 may include cobalt. It can be understood that by preparing cobalt by atomic layer deposition, the controllability of the preparation of the liner layer 130 can be improved to obtain a thinner and more uniform liner layer 130.
  • the thickness of the liner layer 130 may be controlled to be 1 nm to 10 nm.
  • plasma bombardment may be used to clean the surface of the barrier layer 120 , thereby reducing the difficulty of preparing the liner layer 130 .
  • the material of the liner layer 130 may also be deposited outside the interconnection groove 111 .
  • Step S3 preparing a metal interconnection layer in the interconnection groove.
  • Fig. 5 is a schematic diagram showing a structure of preparing a metal seed layer 140 and a metal interconnection layer 150 based on the structure shown in Fig. 4. As shown in Fig. 5, the metal seed layer 140 is stacked on the liner layer 130, and the metal interconnection layer 150 is prepared in the interconnection groove 111 and stacked on the liner layer 130.
  • the method of preparing the metal interconnection layer 150 may be selected from the electroplating method.
  • the electroplating method can make the metal interconnection layer 150 as uniformly and fully filled in the interconnection groove 111 as possible.
  • a step of preparing a metal seed layer 140 in the interconnection groove 111 is also included.
  • the metal seed layer 140 can be used as a seed when preparing the metal interconnection layer 150, so that the metal interconnection layer 150 can be more fully filled in the interconnection groove 111.
  • the metal seed layer 140 may be prepared by a physical vapor deposition method.
  • the material of the metal seed layer 140 is the same as the material of the metal interconnection layer 150 .
  • the material of the metal interconnection layer 150 may be selected from one or more of platinum, cobalt, copper and ruthenium. In this embodiment, the material of the metal interconnection layer 150 is copper.
  • the materials of the metal seed layer 140 and the metal interconnection layer 150 may also be deposited outside the interconnection groove 111. Therefore, in some examples of this embodiment, after the metal interconnection layer 150 is prepared, a step of planarizing the dielectric layer 110 and the structure located on the dielectric layer 110 is also included to remove the materials of the metal interconnection layer 150, the metal seed layer 140, the liner layer 130 and the barrier layer 120 located outside the interconnection groove 111.
  • FIG6 is a schematic diagram showing a structure after planarization processing is performed on the basis of the structure shown in FIG5.
  • the top surface of the metal interconnection layer 150 is flush with the notch of the dielectric layer 110 .
  • the top surfaces of the metal seed layer 140 , the liner layer 130 , and the barrier layer 120 are also flush with the notch of the dielectric layer 110 .
  • the planarization process may be performed by chemical mechanical polishing (CMP).
  • CMP chemical mechanical polishing
  • the dielectric layer 110 and the layer structure on its surface are processed by chemical mechanical polishing, so that the processed dielectric layer 110 and the metal interconnect layer 150 are as flat as possible, which is convenient for the subsequent preparation of the cobalt metal layer 160.
  • Step S4 preparing a cobalt metal layer on the metal interconnection layer.
  • Fig. 7 is a schematic diagram showing a structure of preparing a cobalt metal layer 160 based on the structure shown in Fig. 6. As shown in Fig. 7, the cobalt metal layer 160 is stacked on the metal interconnection layer 150, and the dielectric layer does not have the cobalt metal layer 160.
  • the cobalt metal layer 160 can be prepared by atomic layer deposition of a cobalt organic compound.
  • the structure of the cobalt organic compound has the following general formula:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from R 5 substituted or unsubstituted C1-C20 alkyl, R 5 substituted or unsubstituted C2-C20 alkenyl, R 5 substituted or unsubstituted C2-C20 alkynyl, R 5 substituted or unsubstituted C3-C20 cycloalkyl;
  • L1 and L2 are each independently selected from R5 substituted or unsubstituted C1-C20 alkylene, R5 substituted or unsubstituted C2-C20 alkenylene, R5 substituted or unsubstituted C2-C20 alkynylene , R5 substituted or unsubstituted C3-C20 cycloalkylene;
  • Each occurrence of R 5 is independently selected from a halogen atom, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a C1-C10 haloalkoxy group or a C6-C20 aryl group.
  • the cobalt atom is bonded to four nitrogen atoms by single bonds, and the four nitrogen atoms form pairs, and the two nitrogen atoms in a pair are connected by an organic chain segment, and each nitrogen atom may also be connected to a substituent.
  • the cobalt organic compound shown in formula (1) can be used as a cobalt precursor for preparing cobalt metal.
  • the cobalt organic compound can be used as a raw material in an atomic layer deposition method, and cobalt metal is generated during the deposition process.
  • the cobalt organic compound when the cobalt organic compound generates cobalt metal in the deposition reaction, the cobalt atoms have a high selectivity for the deposition substrate, and the cobalt atoms have a high selectivity for the deposition substrate. It will be deposited on the surface of metal materials such as copper, platinum and ruthenium, but will not be deposited on the surface of some non-metallic dielectric materials such as silicon and silicon dioxide.
  • the present disclosure conceives of applying the cobalt precursor to the preparation of metal interconnect structures.
  • Cobalt metal is usually used as a barrier material to prevent the diffusion of metal atoms in metal interconnect structures.
  • the application of the cobalt organic compound in the preparation of metal interconnect structures can utilize the selectivity of the cobalt organic compound for the deposition substrate to improve the controllability of the preparation of the cobalt metal layer in the metal interconnect structure.
  • R 1 , R 2 , R 3 and R 4 are selected from the same group, for example, R 1 , R 2 , R 3 and R 4 are collectively isopropyl or tert-butyl.
  • L1 and L2 are also selected from the same group, for example, L1 and L2 can be 1,1-ethylene, 1,2-ethylene, 1,2-vinylene or ethynylene.
  • the cobalt precursor is selected from one of the following structures:
  • the cobalt organic compound having the above structure is particularly suitable for the atomic layer deposition method, and can be selectively deposited on the metal interconnect layer 150 to form a cobalt metal layer 160 with a cobalt atomic content exceeding 90%, while no deposition occurs on the dielectric layer 110.
  • the cobalt organic compound can be used to realize the layer-by-layer preparation of the cobalt metal layer 160 in the form of the atomic layer deposition method, thereby improving the controllability of the cobalt metal layer 160 in terms of film thickness and film uniformity, and is also conducive to obtaining a cobalt metal layer 160 with higher quality to meet the needs of smaller size devices.
  • the atomic layer deposition method is a method of forming a deposited film by alternately passing a gas phase precursor pulse into a reactor and chemically adsorbing and reacting on a deposition substrate. Therefore, the atomic layer deposition method requires the use of raw materials, which should include the above-mentioned cobalt organic compound. It can be understood that in the process of preparing a cobalt metal film using the cobalt organic compound, a reactant that can react with the cobalt precursor is usually required.
  • the cobalt organic compound can be selectively adsorbed on the metal interconnect layer, if a more uniform cobalt film with lower roughness and a higher proportion of cobalt atoms is to be prepared, it is also necessary to ensure the uniform deposition of cobalt atoms in the process of forming cobalt atoms from the cobalt organic compound, otherwise the quality of the cobalt film will still be difficult to improve.
  • the raw materials further include a reaction material capable of reacting with the cobalt organic compound, and the reaction material includes one or more of tert-butylamine (C(CH 3 ) 3 NH 2 ) and diethylamine ((CH 3 CH 2 ) 2 NH).
  • the reaction of the reaction material with the cobalt organic compound is more conducive to uniform deposition of cobalt atoms, so as to obtain a cobalt film with lower thickness, lower surface roughness and higher proportion of cobalt atoms.
  • the process of depositing the cobalt metal layer includes one or more deposition cycles, each deposition cycle includes introducing a cobalt organic compound, purging the cobalt organic compound, introducing a reaction material, and purging the reaction material, wherein the duration of introducing the cobalt organic compound is 1s to 30s, the duration of purging the cobalt organic compound is 1s to 30s, the duration of introducing the reaction material is 1s to 30s, and the duration of purging the reaction material is 1s to 30s.
  • a protective gas may be used to purge the cobalt organic compound and the reaction material, and the protective gas may be one or more of nitrogen, helium, neon, and argon.
  • the role of introducing the cobalt organic compound is to make the cobalt organic compound adsorbed on the surface of the substrate to be coated, and the role of purging the cobalt organic compound is to remove the excess cobalt organic compound in the reaction chamber. Only the cobalt organic compound adsorbed on the surface of the substrate to be coated is retained.
  • the cobalt organic compound can be controlled to fully and selectively adhere to the metal interconnect layer 150 as much as possible.
  • the role of the introduction of the reaction material is to react with the attached cobalt organic compound and generate cobalt metal atoms, and the role of the purging of the reaction material is to clean the reaction chamber and prepare for the next deposition cycle. Controlling the duration of the introduction of the reaction material can allow the cobalt organic compound to fully react to form a cobalt metal layer 160 that completely covers the metal interconnect layer 150.
  • the number of deposition cycles is ⁇ 300.
  • the atoms of the prepared cobalt metal layer 160 may gradually diffuse to the surface of the dielectric layer 110, and the surface state of the dielectric layer 110 may also change, thereby causing the selectivity of cobalt to decrease during the deposition process. Therefore, by controlling the number of deposition cycles to ⁇ 300, it is possible to ensure that the cobalt metal layer 160 is not deposited on the surface of the dielectric layer 110 as much as possible.
  • the number of deposition cycles may be controlled to be ⁇ 300. Further, the number of deposition cycles may be controlled to be 10 to 300. For example, the number of deposition cycles may be 10, 30, 50, 100, 150, 200, 250, 300. The number of deposition cycles may also be a range between the above numbers.
  • the material of the dielectric layer 110 as a silicon-based material, it is also beneficial to avoid the deposition of cobalt atoms on the dielectric layer 110 during the preparation process of the cobalt metal layer 160 .
  • the reaction temperature of the deposition process is controlled to be 100° C. to 400° C.
  • the cobalt metal layer 160 can be deposited as evenly as possible, and the deposition rate of the cobalt metal layer 160 can also be controlled.
  • the thickness of the cobalt metal layer 160 is controlled to be 1 nm to 30 nm.
  • the process of depositing the cobalt metal layer 160 can be performed in an atmosphere of reducing gas to ensure the uniformity of the cobalt metal layer 160.
  • the reducing gas helps to avoid oxidation of the cobalt metal layer 160 during the preparation process, and further avoids the problem of uneven cobalt metal layer 160 caused by selective adsorption and deposition of the cobalt organic compound.
  • a small amount of oxide layer may be generated on the surface of the cobalt metal layer 160.
  • a step of removing the oxide layer on the surface of the cobalt metal layer 160 is also included.
  • the natural oxide layer on the surface of the cobalt metal layer 160 can be removed by plasma treatment of the surface of the cobalt metal layer 160, or by reducing gas treatment of the surface of the cobalt metal layer 160.
  • the reducing gas can be hydrogen.
  • a protective gas such as nitrogen, can also be introduced.
  • a small amount of natural oxide layer may exist on the surface of the metal interconnect layer 150, which may affect the uniformity of the prepared cobalt metal layer 160. Therefore, in some examples of this embodiment, before preparing the cobalt metal layer 160, a step of removing the natural oxide layer on the surface of the metal interconnect layer 150 is also included.
  • the natural oxide layer on the surface of the metal interconnect layer 150 can be removed by plasma treatment of the surface of the metal interconnect layer 150, or by reducing gas treatment of the surface of the metal interconnect layer 150.
  • the reducing gas can be hydrogen.
  • a protective gas such as nitrogen, can also be introduced.
  • the surface roughness of the cobalt metal layer can be controlled to be ⁇ 2 nm, wherein the surface roughness of the cobalt metal layer is defined as the height difference between the highest point and the lowest point of the cobalt metal layer, and the roughness can be obtained by atomic force microscopy.
  • the surface roughness of the cobalt metal layer can be controlled to be ⁇ 1 nm. Further, the surface roughness of the cobalt metal layer can be controlled to be ⁇ 0.5 nm.
  • the cobalt metal layer is prepared using a cobalt organic compound, in the actual preparation product, due to the influence of reaction by-products or the environment of the reaction chamber, the cobalt metal layer does not necessarily include only cobalt atoms, that is, the proportion of cobalt atoms in the cobalt metal layer does not necessarily reach 100%.
  • the cobalt organic compound used in this embodiment can prepare a cobalt metal layer with a higher proportion of cobalt atoms.
  • the proportion of cobalt atoms in the cobalt metal layer is ⁇ 90%. Further, the proportion of cobalt atoms in the cobalt metal layer is ⁇ 95%. Further, the proportion of cobalt atoms in the cobalt metal layer is ⁇ 98%.
  • the cobalt metal layer 160 may also be stacked on the metal seed layer 140 and the liner layer 130. It can be understood that this mainly depends on whether cobalt atoms can be deposited on the metal seed layer 140 and the liner layer 130, but this does not affect the preparation of the cobalt metal layer 160.
  • the material of the pad layer 130 includes cobalt.
  • the cobalt metal layer 160 prepared in this step can be connected to the pad layer 130.
  • the cobalt metal layer 160 and the pad layer 130 together form a cobalt layer surrounding the metal interconnect layer 150, preventing atoms of the metal interconnect layer 150 from diffusing into the surrounding dielectric layer 110.
  • the use of the cobalt organic compound in the atomic layer deposition method can realize the layer-by-layer preparation of the cobalt metal layer 160, improve the controllability of the cobalt metal layer 160 in terms of film thickness and film uniformity, and is also conducive to obtaining a higher quality cobalt metal layer 160 to meet the needs of smaller size devices.
  • steps S1 to S4 the preparation of the metal interconnect structure disclosed in the present invention can be completed.
  • the cobalt metal layer prepared by the atomic layer deposition method using the cobalt organic compound has the characteristics of controllable thickness and uniformity, and is suitable for the preparation of smaller size devices.
  • the present disclosure also provides a method for preparing a metal interconnect structure according to the above embodiment.
  • An embodiment of the metal interconnect structure can be shown in FIG7 .
  • the metal interconnect structure includes: a dielectric layer 110 , a metal interconnect layer 150 , and a cobalt metal layer 160 ;
  • the dielectric layer 110 has an interconnection groove 111 therein, the metal interconnection layer 150 is located in the interconnection groove 111 , and the cobalt metal layer 160 is located on the surface of the metal interconnection layer 150 and does not contact the dielectric layer 110 .
  • the thickness of the cobalt metal layer 160 is ⁇ 30 nm, and the surface roughness of the cobalt metal layer 160 is ⁇ 2 nm.
  • the surface roughness of the cobalt metal layer 160 is defined as the height difference between the highest point and the lowest point of the cobalt metal layer 160, and the roughness can be obtained by atomic force microscopy.
  • the roughness of the surface of the cobalt metal layer 160 is ⁇ 1 nm. Further, the roughness of the surface of the cobalt metal layer 160 is ⁇ 0.5 nm.
  • the thickness of the cobalt metal layer 160 is 1 nm to 10 nm.
  • the thickness of the cobalt metal layer 160 can be 1 nm, 2 nm, 3 nm, 5 nm, 8 nm, 10 nm.
  • the thickness of the cobalt metal layer 160 can also be in the range between the above thicknesses.
  • the proportion of cobalt atoms in the cobalt metal layer 160 is ⁇ 90%. Further, the proportion of cobalt atoms in the cobalt metal layer 160 is ⁇ 95%. Further, the proportion of cobalt atoms in the cobalt metal layer 160 is ⁇ 98%.
  • the surface roughness of the prepared cobalt metal layer 160 is usually more than 2nm due to the limitation of the precision of chemical vapor deposition. Moreover, if a void-free thin film is to be obtained, the thickness of the cobalt metal layer 160 prepared by chemical vapor deposition usually needs to reach more than 30nm. In addition, the proportion of cobalt atoms in the cobalt metal layer 160 prepared by chemical vapor deposition is usually less than 90%.
  • the present disclosure uses the above-mentioned cobalt organic compound to achieve selective atomic layer deposition of the cobalt metal layer 160. Thanks to the characteristics of layer-by-layer deposition of cobalt atoms during the atomic layer deposition process, by selecting appropriate reaction materials and preparation processes, when the thickness of the cobalt metal layer 160 reaches 30nm, its roughness can also be controlled below 2nm, and the proportion of cobalt atoms in the cobalt metal layer 160 can reach more than 90%. Therefore, compared with traditional technologies, the application provided by the present disclosure can effectively improve the controllability of the cobalt metal layer 160 during the preparation process, and the quality of the film can also be effectively improved.
  • the metal interconnect structure may also include a barrier layer 120, a pad layer 130 and a metal seed layer 140 arranged between the metal interconnect layer 150 and the dielectric layer 110, and the barrier layer 120, the pad layer 130 and the metal seed layer 140 are stacked in sequence from the dielectric layer 110 to the metal interconnect layer 150.
  • the present disclosure also provides a semiconductor component, which includes the above-mentioned metal interconnection structure and a plurality of semiconductor devices, and the plurality of semiconductor devices are electrically connected through the metal interconnection structure.
  • the semiconductor component may be an integrated circuit, such as a logic chip or a memory.
  • the semiconductor component may be a memory.
  • the substrate used in each embodiment and comparative example includes: a dielectric layer, the material of the dielectric layer is silicon dioxide.
  • the dielectric layer has an interconnection groove, and the groove wall of the interconnection groove is sequentially stacked with a barrier layer, a liner layer, a metal seed layer and a metal interconnection layer.
  • the barrier layer includes a stacked tantalum/tantalum nitride film, the liner layer includes a cobalt film, the metal seed layer and the metal interconnection layer are made of copper, and the surface of the metal interconnection layer is flush with the surface of the dielectric layer.
  • the substrate is placed in an atomic layer deposition chamber, a cobalt organic compound and tert-butylamine are used as reactants, argon is used as a purge gas, and in each deposition cycle, the duration of the cobalt organic compound is controlled to be 3s, the duration of the purge of the cobalt organic compound is 10s, the duration of the reaction material is controlled to be 5s, the duration of the purge of the reaction material is 15s, and a cobalt metal layer is deposited on the substrate at 200°C, and the number of deposition cycles is 100. After the deposition is completed, it is taken out.
  • the structural formula of the cobalt organic compound used in Example 1 is as follows:
  • the substrate is placed in an atomic layer deposition chamber, a cobalt organic compound and tert-butylamine are used as reactants, argon is used as a purge gas, and in each deposition cycle, the duration of the cobalt organic compound is controlled to be 3s, the duration of the purge is 10s, the duration of the reaction material is controlled to be 5s, the duration of the purge reaction material is 15s, and a cobalt metal layer is deposited on the substrate at 200°C, and the number of deposition cycles is 100. After the deposition is completed, it is taken out.
  • the structural formula of the cobalt organic compound used in Example 2 is as follows:
  • the substrate is placed in an atomic layer deposition chamber, a cobalt organic compound and tert-butylamine are used as reactants, argon is used as a purge gas, in each deposition cycle, the duration of the cobalt organic compound is controlled to be 3s, the duration of the purge of the cobalt organic compound is 10s, the duration of the reaction material is controlled to be 5s, the duration of the purge of the reaction material is 15s, a cobalt metal layer is deposited on the substrate at 200°C, the number of deposition cycles is 100; after the deposition is completed, it is taken out.
  • the structural formula of the cobalt organic compound used in Example 3 is as follows:
  • the cobalt organic compound provided in the embodiment of the present disclosure can be selectively deposited on the metal interconnect layer by atomic layer deposition. Moreover, when the thickness of the prepared cobalt metal layer is 10nm, its roughness can be controlled below 1nm, and the cobalt atomic content in the cobalt metal layer reaches more than 90%. It can be understood that for other cobalt organic compounds with similar structures, the prepared cobalt metal layer also has similar effects. Therefore, the present disclosure will Cobalt organic compounds are used in the preparation of metal interconnect structures.
  • the selectivity of cobalt organic compounds for deposition substrates can be utilized to improve the controllability of the preparation of cobalt metal in metal interconnect structures, improve the controllability of the preparation of cobalt films and the quality of the films, thereby meeting the needs of smaller devices.
  • the execution of the steps described is not strictly limited in order, and the steps may be executed in other orders. Moreover, at least a portion of the steps described may include multiple sub-steps or multiple stages, and these sub-steps or stages are not necessarily executed at the same time, but may be executed at different times, and the execution order of these sub-steps or stages is not necessarily sequential, but may be executed in turn or alternately with other steps or at least a portion of the sub-steps or stages of other steps.

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Abstract

本申请涉及一种金属互连结构的制备方法、金属互连结构及半导体组件。该金属互连结构的制备方法包括如下步骤：提供电介质层(110)，电介质层(110)中具有互连凹槽(111)；在互连凹槽(111)中制备金属互连层(150)；以及，采用包括钴有机化合物的原料，通过原子层沉积法在金属互连层(150)上制备钴金属层(160)。

Description

金属互连结构的制备方法、金属互连结构及半导体组件
相关申请
本公开实施例要求2023年5月9日申请的，申请号为CN202310516214.3，名称为“金属互连结构的制备方法、金属互连结构及半导体组件”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本公开涉及金属互连技术领域，尤其涉及一种金属互连结构的制备方法、金属互连结构及半导体组件。
背景技术
金属互连结构是半导体器件中的一种常见结构，金属互连结构通常包括介质层和被介质层隔开的互连线，互连线通常用于在多个器件之间实现电连接，为了提高互连线的导电性，互连线的材料通常为金属，例如铜。金属的原子容易扩散至介质层中，这可能会导致器件失效，因此金属互连结构通常还会在介质层与互连线之间引入阻挡层。
目前通常采用化学气相沉积法制备钴膜作为阻挡层材料。然而，随着集成电路制造工艺的不断发展，半导体器件的关键尺寸也在不断缩小，钴膜制备的可控程度以及薄膜质量也逐渐难以满足半导体器件的需要。
发明内容
根据本公开的一些实施例，提供了一种金属互连结构的制备方法，其包括如下步骤：
提供电介质层，所述电介质层中具有互连凹槽；
在所述互连凹槽中制备金属互连层；以及，
采用包括钴有机化合物的原料，通过原子层沉积法在所述金属互连层上制备钴金属层，在所述钴有机化合物中，钴原子与四个氮原子以单键键合，四个所述氮原子两两成对，每对所述氮原子之间以有机基团相连接。
在本公开的一些实施例中，所述钴有机化合物具有如通式(1)所示的结构：
其中，R1、R2、R3和R4各自独立地选自取代或未取代的C1～C20的烷基、取代或未取代的C2～C20的烯基、取代或未取代的C2～C20的炔基、取代或未取代的C3～C20的环烃基；
L1和L2各自独立地选自取代或未取代的C1～C20的亚烷基、取代或未取代的C2～C20的亚烯基、取代或未取代的C2～C20的亚炔基；
且当R1、R2、R3、R4、L1和L2的基团存在取代时，取代基包括R5，R5每次出现，独立地选自烷基、卤原子、C1～C10的烷氧基、C1～C10的卤代烷基、C1～C10的卤代烷氧基或C6～C20的芳基。
在本公开的一些实施例中，R1、R2、R3和R4各自独立地选自正丙基、异丙基、正丁基、异丁基或叔丁基。
在本公开的一些实施例中，L1和L2各自独立地选自亚甲基、1,2-亚乙基、1,1-亚乙基、1,2-亚乙烯基或乙炔基。
在本公开的一些实施例中，R1和R2为相同的基团。
在本公开的一些实施例中，R3和R4为相同的基团。
在本公开的一些实施例中，L1和L2为相同的基团。
在本公开的一些实施例中，所述钴有机化合物选自如下结构之一：

在本公开的一些实施例中，在制备所述钴金属层的步骤中，所述原料还包括能够与所述钴有机化合物反应的反应物料，所述反应物料包括叔丁基胺和二乙胺中的一种或多种。
在本公开的一些实施例中，在沉积所述钴金属层的过程中，控制沉积过程的反应温度为100℃～400℃。
在本公开的一些实施例中，沉积钴金属层的过程包括一个或多个沉积循环，每一个沉积循环包括通入钴有机化合物、吹扫钴有机化合物、通入反应物料以及吹扫反应物料，其中，通入钴有机化合物的持续时间为1s～30s，吹扫钴有机化合物的持续时间为1s～30s，通入反应物料的持续时间为1s～30s，吹扫反应物料的持续时间为1s～30s。
在本公开的一些实施例中，在沉积钴金属层的过程中，控制沉积循环的数量≤300。
在本公开的一些实施例中，沉积钴金属层的过程在还原性气体的氛围中进行。
在本公开的一些实施例中，在沉积钴金属层之后，还包括采用还原性气体或等离子体处理所述钴金属层。
在本公开的一些实施例中，所述电介质层的材料选自二氧化硅、硅基聚合物材料和碳掺杂氧化硅中的一种或多种。
在本公开的一些实施例中，所述金属互连层的材料选自铂、钴、铜和钌中的一种或多种。
在本公开的一些实施例中，在所述互连凹槽中制备金属互连层之前，还包括：
制备覆盖所述互连凹槽槽壁的阻挡层；
在所述阻挡层上制备衬垫层，所述金属互连层制备于所述衬垫层上。
进一步地，本公开还提供了一种金属互连结构，所述金属互连结构包括：电介质层、金属互连层和钴金属层；所述电介质层中具有互连凹槽，所述金属互连层位于所述互连凹槽中，所述钴金属层设置于所述金属互连层上，所述钴金属层通过原子层沉积法在所述金属互连层上制备。
在本公开的一些实施例中，在制备所述钴金属层的步骤中，所述原料还包括能够与所述钴有机化合物反应的反应物料，所述反应物料包括叔丁基胺和二乙胺中的一种或多种。
在本公开的一些实施例中，在所述原料中，在沉积所述钴金属层的过程中，控制沉积过程的反应温度为100℃～400℃。
在本公开的一些实施例中，所述钴金属层的厚度≤30nm，且所述钴金属层的表面的粗糙度≤2nm。
在本公开的一些实施例中，所述钴金属层中钴原子的占比≥90％。
在本公开的一些实施例中，所述电介质层的材料选自二氧化硅、硅基聚合物材料和碳掺杂氧化硅中的一种或多种。
在本公开的一些实施例中，所述金属互连层的材料选自铂、钴、铜和钌中的一种或多种。
在本公开的一些实施例中，所述金属互连结构还包括设置于所述金属互连层与所述电介质层之间的阻挡层、衬垫层和金属种子层，所述阻挡层、所述衬垫层和所述金属种子层自所述电介质层至所述金属互连层的方向依次叠置。
进一步地，本公开还提供了一种半导体组件，所述半导体组件包括如上述任意实施例所述的金属互连结构以及多个半导体器件，多个所述半导体器件之间通过所述金属互连结构电连接。
在本公开的一些实施例中，所述半导体组件为存储器。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他实施例的附图。
图1为本公开的一种金属互连结构的制备方法的步骤示意图；
图2为本公开提供的电介质层的结构示意图；
图3为在图2所示结构的基础上制备阻挡层的结构示意图；
图4为在图3所示结构的基础上制备衬垫层的结构示意图；
图5为在图4所示结构的基础上制备金属种子层和金属互连层的结构示意图；
图6为在图5所示结构的基础上进行平坦化处理后的结构示意图；
图7为在图6所示结构的基础上制备钴金属层的结构示意图；
其中，各附图标记及其含义如下：
110、电介质层；111、互连凹槽；120、阻挡层；130、衬垫层；140、金属种子层；150、金属互连层；160、钴金属层。
具体实施方式
为了便于理解本公开，下面将参照相关附图对本公开进行更全面的描述。附图中给出了本公开的首选实施例。但是，本公开可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本公开的公开内容更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本公开的技术领域的技术人员通常理解的含义相同。本文中在本公开的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本公开。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
空间关系术语例如“在...下”、“在...下面”、“下面的”、“在...之下”、“在...之上”、“上面的”等，在这里可为了方便描述而被使用从而描述图中所示的一个元件或特征与其它元件或特征的关系。应当明白，除了图中所示的取向以外，空间关系术语意图还包括使用和操作中的器件的不同取向。例如，如果附图中的器件翻转，然后，描述为“在其它元件下面”或“在其之下”或“在其下”元件或特征将取向为在其它元件或特征“上”。因此，示例性术语“在...下面”和“在...下”可包括上和下两个取向。器件可以另外地取向(旋转90度或其它取向)并且在此使用的空间描述语相应地被解释。
在此使用的术语的目的仅在于描述具体实施例并且不作为本公开的限制。在此使用时，单数形式的“一”、“一个”和“所述/该”也意图包括复数形式，除非上下文清楚指出另外的方式。还应明白术语“组成”和/或“包括”，当在该说明书中使用时，确定所述特征、整数、步骤、操作、元件和/或部件的存在，但不排除一个或更多其它的特征、整数、步骤、操作、元件、部件和/或组的存在或添加。在此使用时，术语“和/或”包括相关所列项目的任何及所有组合。
在本文中，以开放式描述的技术方案中，可以包括包含所列举技术特征的开放式技术方案，也可以包括所列举特征组成的封闭式技术方案。
在本文中，烷基指的是包含伯(正)碳原子、仲碳原子、叔碳原子、季碳原子或其组合的、具有一个键合位点的饱和烃基。烷基可以认为是对应的烷烃中少去一个氢原子并对应产生一个键合位点的烃基。包含该术语的短语，例如“C1～C20的烷基”是烷基部分包含1～20个碳原子。合适的示例包括但不限于：甲基(-CH3)、乙基(-CH2CH3)、1-丙基(正丙基、-CH2CH2CH3)、2-丙基(异丙基、-CH(CH3)2)、1-丁基(正丁基、-CH2CH2CH2CH3)、2-甲基-1-丙基(-CH2CH(CH3)2)、2-丁基(-CH(CH3)CH2CH3)、1,1-二甲基乙基(叔丁基、-C(CH3)3)、1-戊基(正戊基、-CH2CH2CH2CH2CH3)、2-戊基(-CH(CH3)CH2CH2CH3)、3-戊基(-CH(CH2CH3)2)、2-甲基-2-丁基(-C(CH3)2CH2CH3)、3-甲基-2-丁基(-CH(CH3)CH(CH3)2)、3-甲基-1-丁基(-CH2CH2CH(CH3)2)、2-甲基-1-丁基(-CH2CH(CH3)CH2CH3)、1-己基(正己基、-CH2CH2CH2CH2CH2CH3)、2-己基(-CH(CH3)CH2CH2CH2CH3)、3-己基(-CH(CH2CH3)(CH2CH2CH3))、2-甲基-2-戊基(-C(CH3)2CH2CH2CH3)、3-甲基-2-戊基(-CH(CH3)CH(CH3)CH2CH3)、4-甲基-2-戊基(-CH(CH3)CH2CH(CH3)2)、3-甲基-3-戊基(-C(CH3)(CH2CH3)2)、2-甲基-3-戊基(-CH(CH2CH3)CH(CH3)2)、2,3-二甲基-2-丁基(-C(CH3)2CH(CH3)2)、3,3-二甲基-2-丁基(-CH(CH3)C(CH3)3和辛基(-(CH2)7CH3)。
在本文中，亚烷基指的是具有两个键合位点的饱和烃基。亚烷基可以认为是对应的烷烃中少去两个氢原子并对应产生两个键合位点的烃基。包含该术语的短语，例如“C1～C20的亚烷基”是亚烷基部分包含1～20个碳原子。亚烷基可以是在上述烷基的基础上少去一个氢原子并在对应位置形成键合位点的基团。合适的示例包括但不限于：亚甲基(-CH2-)、亚乙基(-CH(CH3)-)和1,2-亚乙基(-CH2CH2-)。
在本文中，烯基也可以称作烯烃基，指的是包含具有一个或多个碳碳双键的、且具有一个键合位点的不饱和烃基。烯基可以认为是对应的烯烃中少去一个氢原子并对应产生一个键合位点的烃基。包含该短语的术语，例如“C1～C20的烯基”是烯基部分包含1～20个碳原子。烯基可以是在上述烷基的基础上少去两个氢原子并使得两个碳原子之间形成双键的烃基。合适的示例包括但不限于：乙烯基(-CH＝CH2)和烯丙基(-CH2CH＝CH2)。
在本文中，亚烯基指的是具有一个或多个碳碳双键的、且具有两个键合位点的不饱和烃基。亚烯基可以认为是对应的烯烃中少去两个氢原子并对应产生两个键合位点的烃基。包含该术语的短语，例如“C1～C20的亚烯基”是亚烯基部分包含1～20个碳原子。亚烯基可以是在上述烯基的基础上少去一个氢原子并在对应位置形成键合位点的基团。合适的示例包括但不限于：1,2-亚乙烯基(-CH＝CH-)和1-甲基-1,2-亚乙烯基(-C(CH3)＝CH-)。
在本文中，炔基也可以称作炔烃基，指的是包含具有一个或多个碳碳三键的、且具有一个键合位点的不饱和烃基。炔基可以认为是对应的炔烃中少去一个氢原子并对应产生一个键合位点的烃基。包含该短语的术语，例如“C1～C20的炔基”是炔基部分包含1～20个碳原子。炔基可以是在上述烷基的基础上少去四个氢原子并使得两个碳原子之间形成三键的烃基。合适的示例包括但不限于：乙炔基(-C≡CH)和炔丙基(-CH2C≡CH)。
在本文中，亚炔基指的是具有一个或多个碳碳三键的、且具有两个键合位点的不饱和烃基。亚炔基可以认为是对应的炔烃中少去两个氢原子并对应产生两个键合位点的烃基。包含该术语的短语，例如“C1～C20的亚炔基”是亚炔基部分包含1～20个碳原子。亚炔基可以是在上述炔基的基础上少去一个氢原子并在对应位置形成键合位点的基团。合适的示例包括但不限于：亚乙炔基(-C≡C-)和亚炔丙基(-CH2C≡C-)。
在本文中，“烷氧基”指的是连接有氧原子的烷基的基团，即如上所定义的烷基经由氧原子连接至母核的结构。“卤代烷氧基”指的是烷氧基中的烷基部分的氢原子由卤原子取代后形成的结构。
在本文中，“卤原子”是指F、Cl、Br或I。
本公开提供了一种金属互连结构的制备方法，其包括如下步骤：
提供电介质层，电介质层中具有互连凹槽；
在互连凹槽中制备金属互连层；以及，
采用包括钴有机化合物的原料，通过原子层沉积法在金属互连层上制备钴金属层，在钴有机化合物中，钴原子与四个氮原子以单键键合，四个氮原子两两成对，每对氮原子之间以有机基团相连接。
其中，金属互连结构指的是同时与多个器件连接的、用于实现导电的结构。在目前的工艺中，金属互连结构通常包括电介质层以及制备于电介质层中的金属互连层。金属互连结构中还包括位于金属互连层上的钴金属层，钴前驱体可以用于制备该钴金属层。
对于制备钴金属层来说，要求钴金属层能够选择性地仅沉积在金属互连层上，而基本不沉积在电介质层上。而受限于具体的原料以及实际的制备工艺，传统技术中仅能够通过化学气相沉积法的方式实现选择性制备，并且一直未能实现通过原子层沉积法的方式进行钴的选择性制备。然而随着器件的关键尺寸的不断缩小，化学气相沉积法的可控性较差、钴薄膜的质量较差等问题都愈发突出。
可以理解，电介质层的材料应当为绝缘材料，通常为非金属的绝缘材料。
其中，具有上述结构的钴有机化合物能够选择性地吸附于不同材质的基底上。具体地，该钴有机化合物能够选择性地吸附于包括铜、钌和铂等在内的金属材料上，而难以吸附至 包括硅、二氧化硅和氮化硅在内的非金属的电介质材料上。原子层沉积法的制备工艺恰好需要前驱体材料先吸附至沉积基底上，因此采用该类钴有机化合物作为前驱体，能够使得钴膜选择性地形成于金属互连层上，而电介质层上基本不具有钴原子或难以形成钴膜。
于本公开提供的金属互连结构的制备方法中，采用包括钴有机化合物的原料，通过原子层沉积法在金属互连层上制备钴金属层，在该钴有机化合物中，钴原子与四个氮原子以单键键合，且四个氮原子两两成对，每对氮原子之间以有机基团相连接。具有上述结构的钴有机化合物能够作为原子层沉积法的反应原料，并且在原子层沉积的过程中，该钴有机化合物能够选择性地吸附于金属互连层上而基本不吸附于电介质层上，使得形成的钴膜也选择性地形成于金属互连层上。相较于传统技术，通过原子层沉积法的方式制备钴膜，能够有效提高钴膜的制备可控性以及薄膜质量。
可以理解，钴膜的制备可控性可以包括钴膜的最小厚度、表面粗糙度以及钴金属层中的钴原子占比等参数。通常，钴膜的制备可控性越高，有利于制备得到更薄的、表面粗糙度更低的和/或钴原子占比更高的钴膜
可以理解，在采用该钴前驱体制备钴金属膜的过程中，通常还需要能够与该钴前驱体发生反应的反应物料。
进一步地，在该实施例的一些示例中，钴有机化合物具有如通式(1)所示的结构：
其中，R1、R2、R3和R4各自独立地选自取代或未取代的C1～C20的烷基、取代或未取代的C2～C20的烯基、取代或未取代的C2～C20的炔基、取代或未取代的C3～C20的环烃基；
L1和L2各自独立地选自取代或未取代的C1～C20的亚烷基、取代或未取代的C2～C20的亚烯基、取代或未取代的C2～C20的亚炔基；
且当R1、R2、R3、R4、L1和L2的基团存在取代时，取代基包括R5，R5每次出现，独立地选自烷基、卤原子、C1～C10的烷氧基、C1～C10的卤代烷基、C1～C10的卤代烷氧基或C6～C20的芳基。
可以理解，式(1)所提供的钴有机化合物中，钴原子以单键与四个氮原子相键合，并 且，四个氮原子两两成对，一对的两个氮原子之间通过有机链段相连接，并且每个氮原子上还可以连接有取代基。
在该实施例的一些示例中，R1、R2、R3和R4可以各自独立地选自C1～C10的烷基、C2～C10的烯基或C2～C10的炔基。进一步地，R1、R2、R3和R4可以各自独立地选自C1～C5的烷基、C2～C5的烯基或C2～C5的炔基。通过选取碳原子数较少的基团，有助于使得钴有机化合物在制备过程中更易于气化并吸附至金属互连层上，提高钴金属层的均匀性和制造效率。
在该实施例的一些示例中，R1、R2、R3和R4各自独立地选自C3～C4的烷基，例如正丙基、异丙基、正丁基、异丁基或叔丁基。其中，正丙基的结构式为-CH2CH2CH3，异丙基的结构式为-CH(CH3)2，正丁基的结构式为-CH2CH2CH2CH3，异丁基的结构式为-CH(CH3)CH2CH3，叔丁基的结构式为-C(CH3)3。
在该实施例的一些示例中，L1和L2各自独立地选自C1～C10的亚烷基、C2～C10的亚烯基或C2～C10的亚炔基。进一步地，R1、R2、R3和R4可以各自独立地选自C1～C5的亚烷基、C2～C5的亚烯基或C2～C5的亚炔基。通过选取较短的链段，有助于提高该钴有机化合物的反应活性，提高钴金属层的均匀性和制造效率。
在该实施例的一些示例中，L1和L2各自独立地选自C1～C2的亚烷基、C2的亚烯基以及C2的亚炔基。例如，L1和L2各自独立地选自亚甲基(-CH2-)、1,2-亚乙基(-CH2CH2-)、1,1-亚乙基(-CH(CH3)-)、1,2-亚乙烯基(-CH＝CH-)或乙炔基(-C≡C-)。
其中，通过如上基团的选取，能够使得该钴前驱体具有较高的反应活性，并且使得反应副产物较为容易被去除。
在该实施例的一些示例中，R1、R2、R3和R4选自相同的基团，例如R1、R2、R3和R4共同为异丙基或叔丁基。
在该实施例的一些示例中，L1和L2也选自相同的基团，例如L1和L2可以共同为1,1-亚乙基、1,2-亚乙基、1,2-亚乙烯基或亚乙炔基。
在该实施例的一些实例中，通式(1)选自如下结构之一：
其中，如上述结构式所示出的钴前驱体，特别适用于原子层沉积法，其能够在例如铂、铜和钌等金属基底上沉积形成钴原子含量超过90％的钴薄膜，而在例如硅和二氧化硅等基 底上不发生沉积。
其中，以结构式为例，以结构式表示L1和L2均为1,2-亚乙烯基(-CH＝CH-)。但得益于较为对称的结构，两对氮原子以及所连接的链段之间能够发生共轭并产生离域电子对，从而使得如上述式中的结构更为稳定。
在该实施例的一些示例中，该金属互连结构的制备过程包括如下步骤：
提供电介质层，电介质层中具有互连凹槽；
在互连凹槽中制备金属互连层；以及，
在金属互连层上制备钴金属层，制备所述钴金属层的步骤包括：采用包括所述钴前驱体的原料，通过原子层沉积法在所述金属互连层上沉积所述钴金属层。
本公开提供的钴前驱体可以作为原子层沉积法所需的钴原料，并且能够选择性地沉积于金属基底上而不沉积于介质层上。相较于传统的化学气相沉积法的制备方式，采用该钴前驱体以原子层沉积法的方式能够实现钴金属层的逐层制备，提高钴金属层在膜层厚度以及薄膜均匀性方面的可控性，并且还有利于获得质量更高的钴金属层，满足更小尺寸器件的需要。
为了便于理解上述钴前驱体在制备金属互连结构中的应用方式，本公开还提供了一种如图1所示的金属互连结构的制备方法的步骤示意图。参照图1所示，该金属互连结构的制备方法包括步骤S1～步骤S5。
步骤S1，提供电介质层。
图2示出了本公开提供的电介质层110的结构示意图。参照图2所示，该电介质层110中设置有互连凹槽111。
可以理解，该互连凹槽111用于供后续制备的金属互连层150填充。图2中示出的互连凹槽111呈多层阶梯状，但在实际的制备过程中，互连凹槽111也可以制备成其他形状，例如孔的截面可以呈梯形状、矩形状或不规则形状，只要能够填充制备金属互连层150即可。
在该实施例的一些示例中，电介质层110的材料可以是低介电常数材料(也称为low-K材料)。例如，电介质层110的材料的介电常数≤3.9。进一步地，电介质层110的材料 的介电常数≤2.8。通过选取介电常数更低的电介质层110材料，能够降低金属互连层150之间的寄生电容。
在该实施例的一些示例中，电介质层110的材料可以包括硅化合物。例如，电介质层110的材料可以选自二氧化硅、硅基聚合物材料、碳掺杂氧化硅和硅基气凝胶中的一种或多种。其中，硅基聚合物材料可以是例如SiLK、HSQ(hydrogen silsesquioxane)和MSQ(methylsilsesquioxane)中的一种或多种。碳掺杂氧化硅可以是例如Black Diamond、Coral和Aurora中的一种或多种。
在该实施例中，电介质层110的材料包括二氧化硅。
步骤S2，在互连凹槽中制备阻挡层和衬垫层。
图3示出了在图2所示结构的基础上制备阻挡层120的结构示意图。参照图3所示，阻挡层120制备于互连凹槽111中，且覆盖互连凹槽111的槽壁。
其中，阻挡层120用于间隔电介质层110以及后续制备的金属互连层150，阻挡金属互连层150中的金属原子向电介质中扩散。
在该实施例的一些示例中，阻挡层120的材料可以包括钽、氮化钽、钛、氮化钛和氮化钛硅中的一种或多种。在该实施例中，阻挡层120的材料可以包括氮化钽。
另外，在该实施例的一些示例中，阻挡层120也可以是多种材料形成的复合层，例如，阻挡层120可以是由钽层和氮化钽层叠置形成的复合层。
在该实施例的一些示例中，制备阻挡层120的方法可以是化学气相沉积法或原子层沉积法。
参照图3所示，在该实施例的一些示例中，在制备阻挡层120时，阻挡层120的材料也可以一并沉积于互连凹槽111之外的电介质层110表面。
阻挡层120的厚度可以根据实际需求进行限制。在该实施例的一些示例中，阻挡层120的厚度可以是0.5nm～10nm。进一步地，阻挡层120的厚度可以是0.5nm～5nm。更进一步地，阻挡层120的厚度可以是0.5nm～3nm。
图4示出了在图3所示结构的基础上制备衬垫层130的结构示意图。参照图4所示，衬垫层130制备于互连凹槽111中，且层叠设置于阻挡层120的表面。
可以理解，衬垫层130也可以用于间隔电介质与后续制备的金属互连层150。另外，衬垫层130还可以作为后续制备的种子层的形核基底，提高后续制备的层的均匀程度以及填空能力。
在该实施例的一些示例中，衬垫层130的材料可以是钴和钌中的一种或多种。
在该实施例的一些示例中，制备衬垫层130的方法可以是化学气相沉积法或原子层沉 积法。
在该实施例的一些示例中，衬垫层130的厚度可以是1nm～10nm。进一步地，衬垫层130的厚度可以是1nm～5nm。更进一步地，衬垫层130的厚度可以是1nm～3nm。
在该实施例的一些示例中，衬垫层130的材料可以包括钴。可以理解，通过采用原子层沉积法的方式制备钴，能够提高衬垫层130的制备可控性，以获得厚度更薄且更为均匀地衬垫层130。
在该实施例的一些示例中，当衬垫层130的材料为钴时，可以控制衬垫层130的厚度为1nm～10nm。
在该实施例的一些示例中，在制备衬垫层130之前，还可以采用等离子体轰击阻挡层120表面，以清洁阻挡层120表面，降低衬垫层130的制备难度。
在该实施例的一些示例中，在制备衬垫层130时，衬垫层130的材料也可以一并沉积于互连凹槽111之外。
步骤S3，在互连凹槽中制备金属互连层。
图5示出了在图4所示结构的基础上制备金属种子层140和金属互连层150的结构示意图。参照图5所示，金属种子层140层叠设置于衬垫层130上，金属互连层150制备于互连凹槽111中且层叠设置于衬垫层130上。
在该实施例的一些示例中，制备金属互连层150的方式可以选自电镀法。电镀法能够使得金属互连层150尽可能均匀且充分地填充于互连凹槽111中。
在该实施例的一些示例中，在制备金属互连层150之前，还包括在互连凹槽111中制备金属种子层140的步骤。金属种子层140可以用作为制备金属互连层150时的种子，以使得金属互连层150能够更为充分地填充于互连凹槽111中。
在该实施例的一些示例中，金属种子层140的制备方式可以选自物理气相沉积法。
在该实施例的一些示例中，金属种子层140的材料与金属互连层150的材料相同。
在该实施例的一些示例中，金属互连层150的材料可以选自铂、钴、铜和钌中的一种或多种。在该实施例中，金属互连层150的材料为铜。
可以理解，在实际的制备过程中，金属种子层140和金属互连层150的材料也可能会沉积于互连凹槽111之外。因此，在该实施例的一些示例中，在制备金属互连层150之后，还包括对电介质层110以及位于电介质层110上的结构进行平坦化处理的步骤，以去除位于互连凹槽111之外的金属互连层150、金属种子层140、衬垫层130和阻挡层120的材料。
图6示出了在图5所示结构的基础上进行平坦化处理后的结构示意图。参照图6所示， 在该实施例的一些示例中，金属互连层150的顶面与电介质层110的槽口齐平。进一步地、金属种子层140、衬垫层130和阻挡层120的顶面也均与电介质层110的槽口齐平。
在该实施例的一些示例中，平坦化处理的方式可以是化学机械抛光法(Chemical Mechanical Polishing，CMP)。采用化学机械抛光法处理电介质层110及其表面上的层结构，能够使得处理后的电介质层110和金属互连层150尽可能平坦，便于后续的钴金属层160的制备。
步骤S4，在金属互连层上制备钴金属层。
图7示出了在图6所示结构的基础上制备钴金属层160的结构示意图。参照图7所示，钴金属层160层叠设置于金属互连层150上，并且介质层上不具有该钴金属层160。
在该实施例中，钴金属层160可以采用钴有机化合物通过原子层沉积法的方式制备。该钴有机化合物的结构具有如下的通式：
其中，R1、R2、R3和R4各自独立地选自R5取代或未取代的C1～C20的烷基、R5取代或未取代的C2～C20的烯基、R5取代或未取代的C2～C20的炔基、R5取代或未取代的C3～C20的环烃基；
L1和L2各自独立地选自R5取代或未取代的C1～C20的亚烷基、R5取代或未取代的C2～C20的亚烯基、R5取代或未取代的C2～C20的亚炔基、R5取代或未取代的C3～C20的亚环烃基；
R5每次出现，各自独立地选自卤原子、C1～C10的烷氧基、C1～C10的卤代烷基、C1～C10的卤代烷氧基或C6～C20的芳基。
可以理解，在该钴有机化合物中钴原子以单键与与四个氮原子相键合，并且，四个氮原子两两成对，一对的两个氮原子之间通过有机链段相连接，并且每个氮原子上还可以连接有取代基。
如式(1)所示的钴有机化合物能够作为制备钴金属的钴前驱体。例如，可以采用该钴有机化合物作为原子层沉积法中的原料，并在沉积过程中生成钴金属。特别的是，当该钴有机化合物在沉积反应中生成钴金属时，钴原子对于沉积基底具有较高的选择性，钴原子 会沉积于例如铜、铂和钌等金属材料的表面，而不会沉积于例如硅和二氧化硅等一些非金属电介质材料的表面。由此，本公开想到了将该钴前驱体应用于制备金属互连结构中。钴金属通常在金属互连结构中作为阻挡金属原子扩散的阻挡材料，将该钴有机化合物应用于金属互连结构的制备中，能够利用钴有机化合物对于沉积基底的选择性，提高钴金属层在金属互连结构中的制备可控性。
在该实施例的一些示例中，R1、R2、R3和R4选自相同的基团，例如R1、R2、R3和R4共同为异丙基或叔丁基。
在该实施例的一些示例中，L1和L2也选自相同的基团，例如L1和L2可以共同为1,1-亚乙基、1,2-亚乙基、1,2-亚乙烯基或亚乙炔基。
在该实施例的一些实例中，该钴前驱体选自如下结构之一：

具有上述结构的钴有机化合物特别适用于原子层沉积法，其能够选择性地在金属互连层150上沉积，并且形成钴原子含量超过90％的钴金属层160，而在电介质层110上不发生沉积。并且，采用该钴有机化合物以原子层沉积法的方式能够实现钴金属层160的逐层制备，提高钴金属层160在膜层厚度以及薄膜均匀性方面的可控性，并且还有利于获得质量更高的钴金属层160，满足更小尺寸器件的需要。
可以理解，原子层沉积法是通过将气相前驱体脉冲交替地通入反应器并在沉积基体上化学吸附并反应而形成沉积膜的一种方法，因而原子层沉积法需要采用原料，该原料应当包括上述钴有机化合物。可以理解，在采用该钴有机化合物制备钴金属膜的过程中，通常还需要能够与该钴前驱体发生反应的反应物料。尽管该钴有机化合物能够选择性地吸附于金属互连层上，但若要制备更均匀、粗糙度更低以及钴原子占比更高的钴膜，还需要在钴有机化合物形成钴原子的过程中保证钴原子的均匀沉积，否则钴膜的质量仍然难以提升。
在该实施例的一些示例中，在制备钴金属层160的过程中，原料还包括能够与所述钴有机化合物反应的反应物料，该反应物料包括叔丁基胺(C(CH3)3NH2)和二乙胺((CH3CH2)2NH)中的一种或多种。通过该反应物料与上述钴有机化合物反应，更有利于钴原子的均匀沉积，以便于获得厚度更低、表面粗糙度更低以及钴原子占比更高的钴膜。
在该实施例的一些示例中，沉积钴金属层的过程包括一个或多个沉积循环，每一个沉积循环包括通入钴有机化合物、吹扫钴有机化合物、通入反应物料以及吹扫反应物料，其中，通入钴有机化合物的持续时间为1s～30s，吹扫钴有机化合物的持续时间为1s～30s，通入反应物料的持续时间为1s～30s，吹扫反应物料的持续时间为1s～30s。其中，可以采用保护性气体吹扫钴有机化合物和吹扫反应物料，保护性气体可以是氮气、氦气、氖气和氩气中的一种或多种。
可以理解，在一个沉积循环中，通入钴有机化合物的作用在于使得钴有机化合物吸附于待镀膜衬底的表面，吹扫钴有机化合物的作用在于去除反应腔室中多余的钴有机化合物， 而只保留吸附于待镀膜衬底表面的钴有机化合物。控制通入钴有机化合物的持续时间以及吹扫钴有机化合物的持续时间，能够尽可能控制钴有机化合物充分且选择性地附着于金属互连层150上。通入反应物料的作用在于与附着的钴有机化合物反应并生成钴金属原子，吹扫反应物料的作用则在于清洗反应腔室并为下一次沉积循环做准备。控制通入反应物料的而持续时间能够使得钴有机化合物充分反应以形成完整覆盖于金属互连层150上的钴金属层160。
在该实施例的一些示例中，在沉积钴金属层160的过程中，沉积循环的数量≤300。当沉积循环过多时，已经制备的钴金属层160的原子可能会逐渐向电介质层110表面扩散，并且电介质层110的表面状态也可能发生改变，进而导致钴在沉积过程中的选择性下降。因此通过控制沉积循环的数量≤300，能够尽可能确保钴金属层160不沉积于电介质层110表面。
在该实施例的一些示例中，在沉积钴金属层160的过程中，可以控制沉积循环的数量≤300。进一步地，可以控制沉积循环的数量为10～300。例如，沉积循环的数量可以是10、30、50、100、150、200、250、300。沉积循环的数量也可以是上述数量之间的范围。
另外，可以理解，通过选取电介质层110的材料为硅基材料，也有利于在钴金属层160的制备过程中避免钴原子在电介质层110上的沉积。
在该实施例的一些示例中，在沉积钴金属层160的过程中，控制沉积过程的反应温度为100℃～400℃。通过控制合适的反应温度，能够使得钴金属层160沉积得尽可能均匀，并且也有利于控制钴金属层160的沉积速率。
在该实施例的一些示例中，在沉积钴金属层160的过程中，控制钴金属层160的厚度为1nm～30nm。
在该实施例的一些示例中，沉积钴金属层160的过程可以在还原性气体的氛围中进行，以保证钴金属层160的均匀性。可以理解，还原性气体有助于避免钴金属层160在制备过程中发生的氧化，并进而避免该钴有机化合物的选择性吸附和沉积导致的钴金属层160不均匀的问题。
在沉积钴金属层160之后，钴金属层160表面也可能会产生少量氧化层。在该实施例的一些示例中，还包括去除钴金属层160表面的氧化层的步骤。
在该实施例的一些示例中，去除钴金属层160表面的自然氧化层方式可以是采用等离子体处理钴金属层160表面，也可以是采用还原性气体处理钴金属层160表面。其中，还原性气体可以是氢气。在采用还原性气体处理金属互连层150的过程中，还可以一并通入保护性气体，例如氮气。
在沉积钴金属层160之前，金属互连层150的表面可能存在少量自然氧化层，这可能会影响制备的钴金属层160的均匀性。因此，在该实施例的一些示例中，在制备钴金属层160之前，还包括去除金属互连层150表面的自然氧化层的步骤。
在该实施例的一些示例中，去除该金属互连层150表面的自然氧化层方式可以是采用等离子体处理金属互连层150表面，也可以是采用还原性气体处理金属互连层150表面。其中，还原性气体可以是氢气。在采用还原性气体处理金属互连层150的过程中，还可以一并通入保护性气体，例如氮气。
在该实施例的一些示例中，在沉积过程中，可以控制钴金属层的表面的粗糙度≤2nm。其中，钴金属层表面的粗糙度定义为钴金属层的最高点与最低点之间的高度差，粗糙度可以通过原子力显微镜测试得到。
在该实施例的一些实例中，在沉积过程中，可以控制钴金属层的表面的粗糙度≤1nm。进一步地，钴金属层的表面的粗糙度≤0.5nm。
可以理解，尽管采用钴有机化合物制备钴金属层，但在实际的制备产物中，受到反应副产物或反应腔室等环境的影响，钴金属层并不一定仅包括钴原子，即钴金属层中钴原子的占比并不一定能够达到100％。
通过选取合适的反应物料，该实施例所用的钴有机化合物能够制备得到较高钴原子占比的钴金属层。在该实施例的一些示例中，钴金属层中钴原子的占比≥90％。进一步地，钴金属层中钴原子的占比≥95％。更进一步地，钴金属层中钴原子的占比≥98％。
在该实施例的一些示例中，钴金属层160还可以层叠设置于金属种子层140和衬垫层130上。可以理解，这主要取决于钴原子是否能够沉积于金属种子层140和衬垫层130上，但这不影响钴金属层160的制备。
另外，在该实施例中，衬垫层130的材料包括钴，该步骤中制备的钴金属层160可以与衬垫层130相连接，钴金属层160与衬垫层130共同形成围绕金属互连层150的钴层，阻止金属互连层150的原子向四周电介质层110中扩散。
相较于传统的化学气相沉积法的制备方式，采用该钴有机化合物以原子层沉积法的方式能够实现钴金属层160的逐层制备，提高钴金属层160在膜层厚度以及薄膜均匀性方面的可控性，并且还有利于获得质量更高的钴金属层160，满足更小尺寸器件的需要。
通过步骤S1～步骤S4，能够完成本公开的金属互连结构的制备。
采用该钴有机化合物通过原子层沉积法的方式制备得到的钴金属层具有厚度可控以及均匀性可控的特点，适用于更小尺寸器件的制备。
进一步地，本公开还提供了一种由上述实施例中的金属互连结构的制备方法制备得到 的金属互连结构。该金属互连结构的一个实施例可以参照图7所示。
参照图7所示，该金属互连结构包括：电介质层110、金属互连层150和钴金属层160；
电介质层110中具有互连凹槽111，金属互连层150位于互连凹槽111中，钴金属层160位于金属互连层150的表面上且不接触电介质层110。
在该实施例的一些示例中，钴金属层160的厚度≤30nm，钴金属层160的表面的粗糙度≤2nm。其中，钴金属层160表面的粗糙度定义为钴金属层160的最高点与最低点之间的高度差，粗糙度可以通过原子力显微镜测试得到。
在该实施例的一些实例中，钴金属层160的表面的粗糙度≤1nm。进一步地，钴金属层160的表面的粗糙度≤0.5nm。
在该实施例的一些示例中，钴金属层160的厚度为1nm～10nm。例如，钴金属层160的厚度可以是1nm、2nm、3nm、5nm、8nm、10nm。钴金属层160的厚度也可以是上述厚度之间的范围。
在该实施例的一些示例中，钴金属层160中钴原子的占比≥90％。进一步地，钴金属层160中钴原子的占比≥95％。更进一步地，钴金属层160中钴原子的占比≥98％。
对于传统技术中通过化学气相沉积法制备的钴金属层160来说，受限于化学气相沉积法的精度，制备的钴金属层160表面的粗糙度通常超过2nm。并且，如果要获得无空洞的薄膜，化学气相沉积法制备的钴金属层160的厚度通常需要达到30nm以上。另外，化学气相沉积法制备的钴金属层160中，钴原子的占比通常也低于90％。
本公开采用上述钴有机化合物实现了钴金属层160的选择性原子层沉积。得益于在原子层沉积过程中逐层钴原子沉积的特点，通过选取合适的反应物料及制备工艺，在该钴金属层160的厚度达到30nm时，其粗糙度也能够控制在2nm以下，钴金属层160中钴原子的占比能够达到90％以上。因此，相较于传统技术，本公开提供的应用能够有效提高钴金属层160在制备过程中的可控程度，薄膜的质量也能够得到有效提高。
在该实施例的一些示例中，该金属互连结构还可以包括设置于金属互连层150与电介质层110之间的阻挡层120、衬垫层130和金属种子层140，阻挡层120、衬垫层130和金属种子层140自电介质层110至金属互连层150的方向依次叠置。
进一步地，本公开还提供了半导体组件，该半导体组件包括上述金属互连结构以及多个半导体器件，多个半导体器件之间通过该金属互连结构电连接。
在该实施例的一些示例中，该半导体组件可以是集成电路，例如逻辑芯片或存储器。
在该实施例的一些示例中，该半导体组件可以是存储器。
为了更易于理解及实现本发明，以下还提供了如下较易实施的、更为具体详细的实施 例及对比例作为参考。通过下述具体实施例和对比例的描述及性能结果，本发明的各实施例及其优点也将显而易见。在以下各试验例与对比例中，如无特殊说明，以下各实施例和对比例所用的原材料皆可从市场上常规购得。
其中，各实施例和对比例所用的衬底包括：电介质层，电介质层的材料为二氧化硅。电介质层中具有互连凹槽，互连凹槽的槽壁上依次层叠设置有阻挡层、衬垫层、金属种子层和金属互连层。其中，阻挡层包括叠置的钽/氮化钽薄膜，衬垫层包括钴薄膜，金属种子层和金属互连层的材料为铜，金属互连层的表面与电介质层的表面相齐平。
实施例1
将衬底置于原子层沉积腔室中，采用钴有机化合物以及叔丁胺作为反应物料，采用氩气作为吹扫气体，在每一个沉积循环中，控制通入钴有机化合物的持续时间为3s，吹扫钴有机化合物的持续时间为10s，控制通入反应物料的持续时间为5s，吹扫反应物料的持续时间为15s，在200℃下于衬底上沉积钴金属层，沉积循环的数量为100。沉积完成后取出。实施例1所用的钴有机化合物的结构式如下：
实施例2
将衬底置于原子层沉积腔室中，采用钴有机化合物以及叔丁胺作为反应物料，采用氩气作为吹扫气体，在每一个沉积循环中，控制通入钴有机化合物的持续时间为3s，吹扫的持续时间为10s，控制通入反应物料的持续时间为5s，吹扫反应物料的持续时间为15s，在200℃下于衬底上沉积钴金属层，沉积循环的数量为100。沉积完成后取出。实施例2所用的钴有机化合物的结构式如下：
实施例3
将衬底置于原子层沉积腔室中，采用钴有机化合物以及叔丁胺作为反应物料，采用氩气作为吹扫气体，在每一个沉积循环中，控制通入钴有机化合物的持续时间为3s，吹扫钴有机化合物的持续时间为10s，控制通入反应物料的持续时间为5s，吹扫反应物料的持续时间为15s，在200℃下于衬底上沉积钴金属层，沉积循环的数量为100；沉积完成后取出。实施例3所用的钴有机化合物的结构式如下：
试验：通过原子力显微镜测试如上各实施例的钴金属层的厚度及表面粗糙度，以及通过原子能谱测试如上各实施例的钴金属层中的钴原子含量，结果可见于表1。
表1
参照表1所示的结果，本公开的实施例中提供的钴有机化合物能够实现以原子层沉积法的方式选择性地沉积于金属互连层上。并且，在制备的钴金属层厚度为10nm的情况下，其粗糙度能够控制在1nm以下，钴金属层中的钴原子含量达到90％以上。可以理解，对于其他类似结构的钴有机化合物，制备的钴金属层也具有类似的效果。因此，本公开将上述 钴有机化合物应用于制备金属互连结构中，能够利用钴有机化合物对于沉积基底的选择性，提高钴金属在金属互连结构中的制备可控性，提高钴膜的制备可控程度以及薄膜质量，进而满足尺寸更小的器件的需求。
请注意，上述实施例仅出于说明性目的而不意味对本公开的限制。
应该理解的是，除非本文中有明确的说明，所述的步骤的执行并没有严格的顺序限制，这些步骤可以以其它的顺序执行。而且，所述的步骤的至少一部分步骤可以包括多个子步骤或者多个阶段，这些子步骤或者阶段并不必然是在同一时刻执行完成，而是可以在不同的时刻执行，这些子步骤或者阶段的执行顺序也不必然是依次进行，而是可以与其它步骤或者其它步骤的子步骤或者阶段的至少一部分轮流或者交替地执行。
本说明书中的各个实施例均采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似的部分互相参见即可。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。

Claims (27)

  1. 一种金属互连结构的制备方法，其包括如下步骤：
    提供电介质层，所述电介质层中具有互连凹槽；
    在所述互连凹槽中制备金属互连层；以及，
    采用包括钴有机化合物的原料，通过原子层沉积法在所述金属互连层上制备钴金属层，在所述钴有机化合物中，钴原子与四个氮原子以单键键合，四个所述氮原子两两成对，每对所述氮原子之间以有机基团相连接。
  2. 根据权利要求1所述的金属互连结构的制备方法，所述钴有机化合物具有如通式(1)所示的结构：
    其中，R1、R2、R3和R4各自独立地选自取代或未取代的C1～C20的烷基、取代或未取代的C2～C20的烯基、取代或未取代的C2～C20的炔基、取代或未取代的C3～C20的环烃基；
    L1和L2各自独立地选自取代或未取代的C1～C20的亚烷基、取代或未取代的C2～C20的亚烯基、取代或未取代的C2～C20的亚炔基；
    且当R1、R2、R3、R4、L1和L2的基团存在取代时，取代基包括R5，R5每次出现，独立地选自烷基、卤原子、C1～C10的烷氧基、C1～C10的卤代烷基、C1～C10的卤代烷氧基或C6～C20的芳基。
  3. 根据权利要求2所述的金属互连结构的制备方法，R1、R2、R3和R4各自独立地选自正丙基、异丙基、正丁基、异丁基或叔丁基。
  4. 根据权利要求2或3所述的金属互连结构的制备方法，L1和L2各自独立地选自亚甲基、1,2-亚乙基、1,1-亚乙基、1,2-亚乙烯基或乙炔基。
  5. 根据权利要求2～4任意一项所述的金属互连结构的制备方法，R1和R2为相同的基团。
  6. 根据权利要求2～5任意一项所述的金属互连结构的制备方法，R3和R4为相同的基团。
  7. 根据权利要求2～6任意一项所述的金属互连结构的制备方法，L1和L2为相同的基团。
  8. 根据权利要求2所述的金属互连结构的制备方法，所述钴有机化合物选自如下结构之一：
  9. 根据权利要求1～8任意一项所述的金属互连结构的制备方法，在制备所述钴金属层的步骤中，所述原料还包括能够与所述钴有机化合物反应的反应物料，所述反应物料包括叔丁基胺和二乙胺中的一种或多种。
  10. 根据权利要求1～9任意一项所述的金属互连结构的制备方法，在沉积所述钴金属层的过程中，控制沉积过程的反应温度为100℃～400℃。
  11. 根据权利要求1～10任意一项所述的金属互连结构的制备方法，沉积钴金属层的过 程包括一个或多个沉积循环，每一个沉积循环包括通入钴有机化合物、吹扫钴有机化合物、通入反应物料以及吹扫反应物料，其中，通入钴有机化合物的持续时间为1s～30s，吹扫钴有机化合物的持续时间为1s～30s，通入反应物料的持续时间为1s～30s，吹扫反应物料的持续时间为1s～30s。
  12. 根据权利要求1～11任意一项所述的金属互连结构的制备方法，在沉积钴金属层的过程中，控制沉积循环的数量≤300。
  13. 根据权利要求1～12任一项所述的金属互连结构的制备方法，沉积钴金属层的过程在还原性气体的氛围中进行。
  14. 根据权利要求1～13任一项所述的金属互连结构的制备方法，在沉积钴金属层之后，还包括采用还原性气体或等离子体处理所述钴金属层。
  15. 根据权利要求1～14任一项所述的金属互连结构的制备方法，所述电介质层的材料选自二氧化硅、硅基聚合物材料和碳掺杂氧化硅中的一种或多种。
  16. 根据权利要求1～15任一项所述的金属互连结构的制备方法，所述金属互连层的材料选自铂、钴、铜和钌中的一种或多种。
  17. 根据权利要求1～16任一项所述的金属互连结构的制备方法，在所述互连凹槽中制备金属互连层之前，还包括：
    制备覆盖所述互连凹槽槽壁的阻挡层；
    在所述阻挡层上制备衬垫层，所述金属互连层制备于所述衬垫层上。
  18. 一种金属互连结构，所述金属互连结构包括：电介质层、金属互连层和钴金属层；所述电介质层中具有互连凹槽，所述金属互连层位于所述互连凹槽中，所述钴金属层设置于所述金属互连层上，所述钴金属层通过原子层沉积法在所述金属互连层上制备。
  19. 根据权利要求18所述的金属互连结构，在制备所述钴金属层的步骤中，所述原料还包括能够与所述钴有机化合物反应的反应物料，所述反应物料包括叔丁基胺和二乙胺中的一种或多种。
  20. 根据权利要求18或19所述的金属互连结构，在所述原料中，在沉积所述钴金属层的过程中，控制沉积过程的反应温度为100℃～400℃。
  21. 根据权利要求18～20任一项所述的金属互连结构，所述钴金属层的厚度≤30nm，且所述钴金属层的表面的粗糙度≤2nm。
  22. 根据权利要求18～21任一项所述的金属互连结构，所述钴金属层中钴原子的占比≥90％。
  23. 根据权利要求18～22任一项所述的金属互连结构，所述电介质层的材料选自二氧化 硅、硅基聚合物材料和碳掺杂氧化硅中的一种或多种。
  24. 根据权利要求18～23任一项所述的金属互连结构，所述金属互连层的材料选自铂、钴、铜和钌中的一种或多种。
  25. 根据权利要求18～24任一项所述的金属互连结构，所述金属互连结构还包括设置于所述金属互连层与所述电介质层之间的阻挡层、衬垫层和金属种子层，所述阻挡层、所述衬垫层和所述金属种子层自所述电介质层至所述金属互连层的方向依次叠置。
  26. 一种半导体组件，所述半导体组件包括根据权利要求18～25任一项所述的金属互连结构以及多个半导体器件，多个所述半导体器件之间通过所述金属互连结构电连接。
  27. 根据权利要求26所述的半导体组件，所述半导体组件为存储器。
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