TW201445002A - Methods for manganese nitride integration - Google Patents

Abstract

Described are methods of forming a semiconductor device. Certain methods comprises depositing a film comprising manganese nitride over a dielectric; depositing a copper seed layer over the film; and depositing a copper fill layer over the copper seed layer. Also described are semiconductor devices. Certain semiconductor devices comprise a low-k dielectric layer; a manganese nitride layer overlying the low-k dielectric layer; a seed layer selected from a copper seed layer or electrochemical deposition seed layer overlying the manganese nitride layer; a copper layer overlying the copper seed layer.

Description

Method for manganese nitride integration

Embodiments of the present invention relate to a barrier layer in a semiconductor device and to integrate it into a semiconductor device. More particularly, embodiments of the invention relate to thin film integration comprising manganese nitride.

Microelectronic devices such as semiconductor or integrated circuits include millions of electronic circuit devices, such as transistors, capacitors, and the like. In order to further increase the device density on the integrated circuit, there is a smaller feature size. In order to achieve these smaller feature sizes, the wires, vias, interconnects, gates, etc. must be reduced. Reliably forming a multilayer interconnect structure is also required to increase circuit density and quality. Advances in manufacturing technology have enabled copper to be used for wires, interconnects, vias, and other structures. However, as the size of the feature structure decreases and copper is used for the interconnect, the electromigration in the interconnect structure becomes a major obstacle that is difficult to overcome.

When the film thickness of tantalum nitride (TaN) is more than 10 angstroms, the copper barrier layer is continuous, wherein the film is continuous. Since the diameter of the Ta atom is about 4 angstroms, the TaN film of about 5 angstroms thick is not continuous. For small nodes that require a thin TaN, TaN itself is a discontinuous film that limits the copper barrier of TaN. Current methods include the Ta layer placed on top of the TaN layer, the Ta layer serving as a wet layer of copper and providing continuity of the barrier film. For smaller nodes (less than 32 nanometers (nm)), this The method will result in greater line resistance and is therefore not an appropriate solution.

Physical vapor deposition (PVD) tantalum nitride (TaN) is a standard diffusion barrier material for copper interconnects. Since the adhesion of copper to TaN is poor, the lining layer can also be used to enhance the durability of the interconnect structure. When the copper interconnect size is reduced to 20 nm, the non-conformal nature of the PVD TaN barrier plus the Ta liner will cause problems such as copper gap fill holes and high line resistance. Atomic Layer Deposition (ALD) TaN is used as an advanced technology with better conformality; however, the quality of ALD TaN films still needs to be significantly improved.

Therefore, there is still a need for an effective copper barrier layer in this field of technology.

One aspect of the invention is directed to a method of forming a semiconductor device comprising depositing a film comprising manganese nitride onto a dielectric; depositing a copper seed layer onto the film; and depositing a copper fill layer onto the copper seed layer. Various embodiments are listed below. It is to be understood that the following examples can be combined not only in the following, but also in other suitable ways in accordance with the scope of the present invention.

In one or more embodiments, the dielectric is a low dielectric constant (k) dielectric. In some embodiments, the method further comprises depositing a pore sealant onto the dielectric prior to depositing the film comprising the manganese nitride. In one or more embodiments, depositing the copper seed layer comprises chemical vapor deposition, atomic layer deposition, physical vapor deposition, or electrochemical deposition. In some embodiments, manganese nitride is deposited by atomic layer deposition. In one or more embodiments, the method further comprises treating the manganese nitride film with an ammonia plasma post treatment. In some embodiments, the manganese nitride and copper seed layers are deposited in the same chamber. In one or more embodiments, the manganese nitride has a chemical formula of Mn ₃ N ₂ .

A second aspect of the invention relates to a method of forming a semiconductor device comprising depositing a film comprising manganese nitride onto a dielectric; depositing a film comprising cobalt or germanium onto a film comprising manganese nitride, or cobalt or a germanium-doped manganese nitride layer; a copper seed layer deposited; and a copper fill layer deposited onto the copper seed layer.

In one or more embodiments, the dielectric is a low-k dielectric. In some embodiments, the method further comprises depositing a pore sealant onto the low-k dielectric prior to depositing the film comprising the manganese nitride. In one or more embodiments, depositing the copper seed layer comprises chemical vapor deposition, atomic layer deposition, physical vapor deposition, or electrochemical deposition. In some embodiments, manganese nitride is deposited by atomic layer deposition. In one or more embodiments, the method further comprises treating the manganese nitride film with an ammonia plasma post treatment. In some embodiments, the manganese nitride and copper seed layers are deposited in the same chamber. In one or more embodiments, depositing manganese nitride and depositing a film comprising cobalt or ruthenium is performed without breaking the vacuum. In some embodiments, the manganese nitride has a chemical formula of Mn ₃ N ₂ .

A further aspect of the invention relates to a semiconductor device comprising: a low-k dielectric; a manganese nitride layer on a low-k dielectric; a seed layer selected from a copper seed layer or an electrochemically deposited seed layer And located on the manganese nitride layer; the copper layer is located on the copper seed layer. In one or more embodiments, the semiconductor device further comprises a cobalt or germanium containing layer on the manganese nitride layer but below the seed layer. In some embodiments, the seed layer comprises a copper seed layer.

100‧‧‧Microelectronics

105‧‧‧Substrate

110‧‧‧ dielectric layer

115‧‧‧ side wall

120‧‧‧ bottom

130‧‧‧Barrier layer

140‧‧‧Electrical filling material

150‧‧‧ trench

160‧‧‧ openings

200‧‧‧Low k dielectric

210‧‧‧Pore sealant

220‧‧‧Manganese nitride film

230‧‧‧ copper seed layer

240‧‧‧copper filled layer

In order to make the above summary of the present invention more obvious and understood, the description may be made in conjunction with the reference embodiments. It is to be understood that the appended drawings are merely illustrative of exemplary embodiments of the invention Because the invention is susceptible to other equivalent embodiments.

1A and 1B illustrate a dielectric layer before and after deposition of a barrier layer and a conductive filler material in accordance with one or more embodiments of the present invention; and FIG. 2 illustrates one or more embodiments in accordance with the present invention. Semiconductor device.

Before describing several exemplary embodiments of the present invention, it is understood that the invention is not limited to the details of the construction or process steps mentioned below. The invention can be practiced or carried out in various ways.

Embodiments of the present invention relate to thin film integration comprising manganese nitride for use in a post-end interconnect process. This film can be used as a copper barrier and/or copper wetting material during the fabrication of semiconductor devices.

Accordingly, an aspect of the present invention is directed to a method of forming a semiconductor device, the method comprising: depositing a film comprising manganese nitride onto a dielectric; depositing a copper seed layer onto the film; and depositing a copper filled layer to the copper seed On the floor. Several variations of the above methods will be described later.

Manganese nitride is deposited on the dielectric material. The dielectric layer can be provided by methods known in the art. The dielectric layer can be placed on top of other layers as needed. In one or more embodiments, the dielectric comprises a low-k dielectric. The term "low-k dielectric" as used herein refers to a dielectric material having a k value of less than about 4. Examples of low-k dielectrics include fluorinated silicate glass (FSG) (k=3.5), Black Diamond I (k=3.0), Black Diamond IIx (k=2.6), Black Diamond III (k=2.2), But not limited to this. In some embodiments, the dielectric is porous. In this embodiment, the method further comprises depositing before depositing a film comprising manganese nitride The pores are encapsulated onto the dielectric.

In one or more embodiments, "manganese nitride" as used herein may be referred to as "MnN _x ". Depositing a film comprising manganese nitride can be carried out by any suitable method. The deposition method may be atomic layer deposition (ALD) or chemical vapor deposition (CVD). The amount of manganese to nitride can be expressed as a ratio. In one or more embodiments, the atomic ratio of Mn:N is from about 90:10 to about 20:80. Examples of suitable manganese nitride thin film phases include Mn ₄ N, Mn ₃ N ₂ , and Mn ₆ N ₅ , but are not limited thereto. In a further embodiment, Mn: N ratio of about 60:40, and / or phase Mn ₃ N _2.

The manganese nitride layer can be formed by any suitable deposition process. For example, the manganese layer can be deposited by alternating layer deposition (ALD) processes or plasma enhanced atomic layer deposition (PEALD) deposition. The dopant can then be deposited using chemical vapor deposition (CVD), physical vapor deposition (PVD) or ALD. The dopant is then diffused into the manganese-containing layer to form an integrated manganese-containing dopant layer. Different processes, including plasma treatment or heating, can be used to diffuse the dopant into the manganese containing layer.

In some embodiments, the organometallic precursor is deposited MnN _x. In some embodiments, to avoid having the precursor of the oxygen-containing ligands useful, because the oxygen-containing ligands may lead to formation of MnO _x. The manganese oxide formed on the copper surface is difficult to remove, so that the via resistance will be increased. Some precursors have very low vapor pressures and reaction rates, which are challenging in chamber design and poor film morphology during ALD deposition. Some precursor embodiments can utilize CVD to produce high purity manganese films, and ALD to produce high purity MnN _x films with a smooth topography.

The organometallic precursor can include a mercaptoguanamine manganese complex. In some embodiments, in a standard ALD chamber, the trimethyl decyl guanamine manganese complex ALD MnN _x .

In some embodiments, the substrate is brought into contact with the first precursor and the reactants. As in the CVD reaction, the precursors may be substantially simultaneously contacted, or as in the ALD reaction, may be in sequential contact. In a particular embodiment, ALD is used to deposit manganese nitride. The term "substantially simultaneous" as used in this specification and the appended claims means that the precursor and reactant gases flow into the chamber to react with each other and the substrate surface. Those skilled in the art will appreciate that there may be a substrate area that only briefly contacts one of the precursor and reactant gases until the other diffuses into the same area.

In some embodiments, the manganese-containing organometallic compound has the following chemical formula:

A is individually selected from carbon or hydrazine, and R is each selected from hydrogen, methyl, substituted or unsubstituted alkane, branched or unbranched alkane, substituted or unsubstituted olefin, branched or unbranched olefin, substituted or unsubstituted alkyne A hydrocarbon, a branched or unbranched alkyne, or a substituted or unsubstituted aromatic hydrocarbon. The oxidation state of manganese can be any oxidation state suitable for reaction with a substrate or reactant. In some embodiments, the manganese is Mn(II) or Mn(III).

A manganese-containing film can be deposited on the surface of the bare substrate or on the film deposited on the surface of the substrate. For example, a manganese-containing film can be deposited on a dielectric film deposited on a surface. The dielectric film can have various structures (e.g., trenches) with top, bottom, and sidewalls formed therein. In some embodiments, the dielectric film has at least one trench having a sidewall and a bottom. The bottom portion can be a dielectric or dielectric underlying surface (eg, a bare substrate or other material). Manganese-containing films can be selectively deposited on different surfaces. In some embodiments, a manganese-containing film is selectively deposited in the dielectric layer or underlying layer.

In some embodiments, A is a nitrogen atom. In one or more embodiments, the R group is a methyl group. In some embodiments, the manganese-containing organometallic compound comprises bis[bis(trimethyldecyl)decylamine]manganese. In some embodiments, the reactant is one or more ammonia. Although not limited to any particular theory of operation, it is believed that Mn-N will break bonds during film formation. For example, if ammonia is used, a manganese nitride film can be formed.

In some embodiments, the dielectric is porous and requires a pore seal. Examples of suitable methods include ALD SiO ₂ and contacting N ₂ O plasma.

A copper seed layer can be deposited onto a film comprising manganese nitride using methods known in the art. Methods include, but are not limited to, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or electrochemical deposition (ECD).

Depending on the particular deposition mode, it may be advantageous to perform more than one process in the same chamber. In one or more embodiments, the manganese nitride and copper seed layers are deposited in the same chamber. In a further embodiment, such a chamber contains at least two ampoules for different chemicals required during deposition. In an alternate embodiment, the manganese nitride and copper seed layers are deposited in different chambers. In one or more embodiments, depositing manganese nitride and depositing a film comprising cobalt or ruthenium is performed without breaking the vacuum.

After depositing the copper seed layer, a copper fill layer is deposited onto the copper seed layer. This can be done using methods known in the art, including, but not limited to, chemical vapor deposition and physical vapor deposition.

In one or more embodiments, the method further comprises using an ammonia (NH ₃₎ plasma treatment process after manganese nitride film. After depositing the copper fill layer, the surface of the substrate needs to be polished. Post-treatment with ammonia-containing plasma helps to avoid cracking when performing chemical mechanical polishing techniques. The Mn:N ratio was adjusted to a nitrogen-rich ratio during the NH ₃ post treatment. Increasing the nitrogen content of MnN helps to avoid CMP corrosion.

The conditions suitable for the treatment of the ammonia plasma can be selected for the specific film, the precursor used, and the like. Suitable temperatures during contact with the plasma are from about 150 ° C to about 300 ° C. The pressure is approximately from about 0.5 Torr to 10 Torr. The spacing is generally from about 100 mils to about 500 mils. The radio frequency (RF) power at 40 megahertz (MHz) is approximately 100 watts (W) to approximately 1000 W. The NH ₃ flow rate is approximately from about 500 to about 5000 sccm. Rare gas plasma can also be used in the process. For example, argon can be introduced at a flow rate of from about 500 to about 5000 sccm.

In one or more embodiments, the method further comprises depositing a film comprising cobalt or ruthenium onto the film comprising manganese nitride. This can be achieved by methods known in the art.

Alternatively, cobalt or ruthenium may not be a separate layer of separation, but a dopant in the manganese nitride film. According to one or more embodiments of this aspect, the barrier layer comprises manganese nitride and is selected from the group consisting of manganese (Mn), cobalt (Co), ruthenium (Ru), tantalum (Ta), aluminum (Al), and magnesium (Mg). ), a dopant of chromium (Cr), niobium (Nb), titanium (Ti), and vanadium (V). Alternatively, manganese and dopants can be deposited in alternating layers. According to this embodiment, a first manganese-containing layer (e.g., a manganese monolayer) is deposited on the dielectric film. Although a dielectric film is described herein as a lower layer for depositing a manganese-containing film, it should be understood that the lower layer may be any suitable layer, including a metal layer or a base substrate, but is not limited thereto. A first dopant layer (eg, a dopant, a dopant alloy, or other dopant-containing compound layer) is then deposited on top of the first manganese-containing layer. The first dopant layer may also be a single layer. second A manganese containing layer is then deposited on top of the first dopant layer. This process is repeated until a predetermined thickness of the doped manganese-containing film is produced. The manganese-containing layer and the dopant layer may be combined in any suitable ratio and are not limited to 1:1. For example, ten manganese-containing layers can be deposited for each dopant layer.

In some embodiments, more than one precursor gas flows into the processing chamber simultaneously or separately. For example, the manganese-containing precursor and the cobalt precursor can flow together into the chamber to react with the surface. The reactants can be used exclusively for one of the precursor species or for both species. In some embodiments, the substrate or surface contacts the first precursor, then the first reactant, and contacts a second precursor different from the first precursor, then the first reactant or a different one than the first reactant Second reactant.

To deposit the dopant metal, a suitable metal-containing precursor can be used. Examples of suitable precursors include metal complexes containing a predetermined dopant, such as a dopant metal coordinated to an organic or methyl ligand. Suitable dopant precursors preferably have sufficient vapor pressure for deposition in a suitable process, such as ALD, CVD, and PVD. Depending on the dopant precursor used, the co-reactant can be used to deposit dopants. For example, a reducing gas such as hydrogen and ammonia can be used as a co-reactant to deposit some dopants.

Some embodiments of the present invention provide for treating a doped manganese-containing film with a plasma prior to depositing the conductive material. According to one or more embodiments, the plasma contains one or more of He, Ar, NH ₃ , H ₂ and N ₂ . Conductive materials can be deposited in a variety of ways, including electroless deposition processes, electroplating (ECP) processes, CVD processes, or PVD processes. In some embodiments, a first seed layer is deposited on the barrier layer and a bulk conductive layer is then formed on the seed layer.

In one or more embodiments, the barrier layer comprises from 0.1% to 10% by weight of the manganese layer. In some embodiments, the barrier layer comprises 0.2% by weight Up to 8% by weight of dopant. In a particular embodiment, the barrier layer comprises from 0.5% to 5% by weight of dopant.

Another aspect of the invention pertains to a semiconductor device fabricated in the one or more methods. The device will depend on how the method is used. For example, when the method includes depositing a film comprising manganese nitride onto a dielectric; depositing a copper seed layer onto the film; and depositing a copper fill layer onto the copper seed layer, the semiconductor device will comprise the copper seed layer A copper fill layer, a copper seed layer on the film comprising manganese nitride, and a copper seed layer on the dielectric.

In one embodiment, the semiconductor device comprises a low-k dielectric; a manganese nitride layer on the low-k dielectric; and a seed layer selected from the group consisting of a copper seed layer or an electrochemically deposited seed layer and located in the nitride On the manganese layer; the copper layer is on the copper seed layer. In embodiments where the method comprises depositing a layer comprising cobalt or germanium, the semiconductor device will further comprise a layer comprising cobalt or germanium, the layer comprising cobalt or germanium being on the layer of manganese nitride but below the seed layer. In embodiments where the method includes depositing a seed layer, the semiconductor device will further comprise a copper seed layer. In a further embodiment, the seed layer comprises an electrochemically deposited seed layer. In one or more embodiments, the semiconductor device further comprises a pore encapsulant on the low-k dielectric layer but under the manganese nitride layer.

There are many ways to combine the various processes used. For example, the method can include manganese nitride deposition, then ammonia post treatment, copper seed deposition, and then conventional copper plating. In one or more other embodiments, the method comprises manganese nitride deposition, cobalt or tantalum deposition or doping, followed by electrochemical seed deposition, followed by electrochemical plating. In some embodiments, the method comprises manganese nitride deposition followed by cobalt or hafnium deposition or doping followed by copper seeding and electrochemical plating. In one or more embodiments, the method comprises manganese nitride deposition followed by cobalt or hafnium deposition or doping, followed by copper seeding And electrochemically depositing seed crystals, followed by electrochemical plating. The pore seal of the porous dielectric can be performed prior to any of the above steps. Certain portions of the process, such as electrochemical plating and electrochemical deposition, can be performed after vacuum breaking.

FIG. 1A illustrates an embodiment of a microelectronic device 100 that includes a substrate 105 and a dielectric layer 110. Dielectric layer 110 is deposited on substrate 105, which has trenches 150 defined by trench bottoms 120, sidewalls 115, and openings 160.

In one or more embodiments, the dielectric layer 110 is a low-k dielectric layer. In some embodiments, the dielectric layer comprises a porous carbon-doped SiO _x. In one or more embodiments, the dielectric layer is a porous carbon doped SiO _x layer and has a k value of less than 3.

FIG. 1B illustrates the same microelectronic device 100 after deposition of the barrier layer 130, the barrier layer covering at least a portion of the sidewalls 115 and/or the trench bottoms 120. As shown in FIG. 1B, the barrier layer 130 covers the entire sidewall 115 and the trench bottom 120. The barrier layer 130 may comprise MnN _x and one or more dopants such as Co, Mn, Ru, Ta, Al, Mg, Cr, Nb, Ti or V.

In one or more embodiments, the barrier layer comprises from 0.1% to 10% by weight of the manganese layer. In some embodiments, the barrier layer comprises from 0.2% to 8% by weight of dopant. In a particular embodiment, the barrier layer comprises from 0.5% to 5% by weight of dopant.

In accordance with one or more embodiments, the term "barrier layer" as used herein refers to a discontinuous layer formed by depositing TaN and one or more dopants, and excluding the second element or dopant from diffusing only to the portion. The area within the barrier layer. In other words, the dopant system is throughout the thickness of the TaN layer, not just the surface portion of the TaN layer.

The conductive filler material 140 fills at least a portion of the trenches 150, trenches A barrier layer 130 is lined in the trench. According to one or more embodiments, the electrically conductive filler material comprises copper or a copper alloy. In other embodiments, the electrically conductive filler material further comprises aluminum (Al).

Although the conductive fill material 140 of FIG. 1B is shown as directly contacting the barrier layer 130, there may be an intermediate layer, such as an adhesive layer or a seed layer, between the conductive fill material 140 and the barrier layer 130. In accordance with one or more embodiments, the microelectronic device further includes an adhesive layer comprising one or more of Ru, Co, and Mn. In addition to Ru and/or Co, the adhesive layer may comprise one or more dopants such as Ta, Al, Mg, Cr, Nb, Ti or V. In a particular embodiment, the adhesive layer comprises Ru and Mn. In addition to conventional linings, manganese and manganese nitride can be used as a liner. For example, when PVD Cu is replaced by CVD Cu, manganese nitride is preferred as a liner. Further, manganese nitride can be reduced to Mn to serve as a liner to promote adhesion to Cu.

In some embodiments, a seed layer is deposited on top of the barrier layer. According to one or more embodiments, the seed layer comprises a copper alloy, such as a Cu-Mn alloy. In some embodiments, the seed layer comprises less than about 5% by weight Mn, less than about 4% by weight Mn, less than about 3% by weight Mn, or less than about 2% by weight Mn. In one or more embodiments, the seed layer comprises about 1% by weight Mn. The line resistance of a copper alloy containing about 1% by weight of Mn is expected to be the same as or similar to the line resistance of pure copper.

Although not limited to any particular theory, it is believed that the dopant can selectively diffuse through the barrier layer 130 to the dielectric layer 110 and form a complex with the dielectric material that will resist electromigration. Therefore, in some embodiments, Mn and the diffusion barrier layer is formed by MnSiO _x. This self MnSiO _x barrier layer is formed of copper migration can be prevented from electrically conductive material 140 to the dielectric layer 110.

In addition to being a copper barrier, doping manganese can also prevent oxygen from diffusing from the dielectric layer 110 to the conductive material 140. The diffusion of oxygen from the dielectric layer 110 to the conductive material 140 causes oxygen to react with components in the conductive material and/or seed layer. For example, oxygen will react with the layer at the interface of barrier layer 130 and conductive material 140, causing Mn to "pin" into the barrier/conductive material interface. Similarly, if a seed layer containing Mn is present, oxygen reacts with Mn in the seed layer at the interface of the seed layer/barrier layer, and Mn is pinned into the interface.

Figure 2 illustrates another apparatus in accordance with one or more embodiments of the present invention. Figure 2 illustrates a low-k dielectric 200 having a plurality of features (i.e., damascene patterning). As noted above, such low k dielectrics can be porous. As such, the pore sealant 210 can be deposited on the low-k dielectric 200. On the pore sealant 210 is a manganese nitride film 220. The manganese nitride film 220 may be any of the above. A copper seed layer 230 may be deposited on the manganese nitride film 220. The copper fill layer 240 can then be deposited using, for example, a chemical vapor deposition process.

In one or more embodiments, the deposited copper can be subjected to chemical mechanical polishing after the method. The deposited manganese or MnN _x film can be used as an alternating diffusion barrier for the subsequent copper interconnect process to replace the PVD TaN or ALD TaN currently used. The deposition mode can be integrated with ALD TaN deposition to produce manganese doped TaN or MnN _x doped germanium. In an alternate embodiment, TaN and MnN layers can be combined.

Films in accordance with various embodiments of the present invention may actually be deposited on any substrate material. The term "substrate surface" as used herein refers to any substrate that is subjected to film processing during the manufacturing process or the surface of the material formed on the substrate. For example, the surface of the substrate to be processed includes materials such as tantalum, niobium oxide, strain tantalum, insulating layer coating (SOI), carbon-doped tantalum oxide, tantalum nitride, doped germanium, Niobium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. The barrier layer, metal or metal nitride on the surface of the substrate includes titanium, titanium nitride, tungsten nitride, tantalum and tantalum nitride, aluminum, copper or any other conductor that can be used in device fabrication, or a conductive or non-conductive resistive barrier. . The substrate can be of various sizes, such as a wafer having a diameter of 200 millimeters (mm) or 300 mm, and having a rectangular or square pane. Substrates useful in embodiments of the present invention include semiconductor wafers such as crystalline germanium (eg, Si<100> or Si<111>), hafnium oxide, strained germanium, germanium, doped or undoped polysilicon, doped or Undoped germanium wafers, III-V materials (such as GaAs, GaN, InP, etc.) and patterned or unpatterned wafers, but not limited to them. The substrate can be processed by a pretreatment process to grind, etch, reduce, oxidize, hydroxylate, anneal, and/or bake the substrate surface.

Since embodiments of the present invention provide a method of depositing or forming a doped manganese-containing film, the processing chamber can be configured to contact the substrate with a series of gases and/or plasmas during the vapor deposition process. The processing chamber may include a separate reactant supply and any carrier gas, purge gas, and a blunt gas (eg, argon and nitrogen) supply, the carrier gas, the purge gas, and the blunt gas supply fluidly communicate the gases of each reactant and gas Entrance. Each of the inlets may be controlled by a suitable flow controller, such as a mass flow controller or a volume flow controller, which is coupled to a central processing unit (CPU) to permit each reactant stream to the substrate to perform the deposition process. The central processing unit can be any type of computer processor that can be used in industrial settings to control various chambers and sub-processors. The CPU can be coupled to the memory and can be one or more easily accessible memories, such as random access memory (RAM), read only memory (ROM), flash memory, compact disc, soft. Disc, hard drive or any other type of local or remote digital storage. The support circuit can be coupled to the CPU to support the CPU in a conventional manner. These circuits include cache memory, power supplies, clock circuits, input/output circuits, and subsystems.

In an atomic layer deposition type chamber, the substrate may be contacted with the first precursor and the reactant by spatial or temporal separation. Time ALD (also known as time domain ALD) is a conventional process in which a first precursor stream enters a chamber to react with a surface (eg, chemisorption). The first precursor of the chamber is purged prior to flowing the reactants into the chamber. In space ALD, the first precursor and reactant gases flow into the chamber simultaneously, but are spatially separated, so there is an area between the gas streams to prevent precursor mixing. Typically, there will be a gas curtain (e.g., purge gas, vacuum rinse or combination of materials) between the first precursor and the reactants to ensure separation. In space ALD, the substrate must move relative to the gas distribution plate, and vice versa, so that portions of the substrate are exposed to the first precursor and reactant gases.

The substrate can be processed in a single substrate deposition chamber where a single substrate is loaded, processed, and unloaded prior to processing another substrate. The substrate can also be processed in a continuous manner as in a transport system wherein a plurality of substrates are individually loaded into the first portion of the chamber, moved through the chamber, and unloaded from the second portion of the chamber. The shape of the chamber and associated transport system may constitute a straight path or a curved path. Additionally, the processing chamber can be a rotating rack in which a plurality of substrates move about a central axis and contact the deposition gases at different locations.

The co-reactant is usually in the form of a vapor or a gas. The reactants can be transported in the same carrier gas. The carrier gas, purge gas, deposition gas or other process gas may contain nitrogen, hydrogen, argon, helium, neon or a combination of the above. The various plasmas (examples For example, nitrogen plasma or blunt plasma can be ignited by a plasma co-reactant gas and/or contain a plasma co-reactant gas.

In one or more embodiments, various process gases are pulsed to the inlet, through the gas flow path, from different orifices or outlets to the central flow passage. In one or more embodiments, the successive pulses are supplied with a deposition gas and passed through a showerhead. Alternatively, as described above, the gas can flow simultaneously through the gas supply nozzle or head, and the substrate and/or gas supply head can be moved to cause the substrate to contact the gas sequentially.

Another aspect of the invention relates to an apparatus for depositing a film onto a substrate for performing the process according to any of the above embodiments. In one embodiment, the apparatus includes a deposition chamber for depositing a film onto the substrate. The chamber contains a processing area for supporting the substrate. The apparatus includes a precursor inlet fluidly connected to the manganese precursor supply, such as bis[bis(trimethyldecyl)guanamine] manganese. The apparatus also includes a reactant gas inlet, such as ammonia, in fluid communication with the nitrogen-containing precursor supply. The apparatus also includes a reactant gas inlet fluidly connected to the dopant precursor supply, such as a dopant-containing metal complex. The apparatus further includes a purge gas inlet fluidly connected to the purge gas. The apparatus can further include a vacuum port for removing gas from the deposition chamber. The apparatus may further include an auxiliary gas inlet for supplying one or more auxiliary gases to the deposition chamber, such as an blunt gas. The deposition may further comprise means for heating the substrate by radiation and/or resistive heat.

In some embodiments, the plasma system and processing chamber or system available for performing the method to deposit or form a film can be performed on a PRODUCER ^® , CENTURA ^® or ENDURA ^® system, all of which are taken from California, USA. Santa Clara's Applied Materials. A detailed description of the ALD processing chamber can be found in U.S. Patent Nos. 6,821,563, 6,878,206, 6,916,398 and 7,780,785.

In some embodiments, one or more layers may be formed during a plasma enhanced atomic layer deposition (PEALD) process. In some processes, the plasma provides sufficient energy to promote the species to become excited, making the surface reaction beneficial and feasible. The plasma can be introduced into the process either continuously or in a pulsed manner. In some embodiments, the precursor is supplied with a precursor (or reactive gas) and a plasma supplied by a pulse. In some embodiments, the reagent can be ionized locally (ie, within the treatment zone) or distal (ie, outside of the treatment zone). In some embodiments, distal ionization can be performed upstream of the deposition chamber such that ions or other high energy or luminescent species do not directly contact the deposited film. In some PEALD processes, the plasma is generated outside of the processing chamber, such as with a remote plasma generating system. The plasma can be produced using any suitable plasma generating process or by techniques known to those skilled in the art. For example, plasma can be generated by one or more microwave (MW) frequency generators or radio frequency (RF) generators. The plasma frequency can be adjusted depending on the particular reaction species used. Suitable frequencies include 2MHz, 13.56MHz, 40MHz, 60MHz and 100MHz, but not limited to this. Although plasma is used during the deposition process described herein, care should be taken that plasma is not required. In fact, other embodiments are directed to deposition processes in the absence of plasma and under very mild conditions.

According to one or more embodiments, the substrate is processed before and/or after forming the layer. This treatment can be performed in the same chamber or in one or more different processing chambers. In some embodiments, the substrate is moved from the first chamber to a different second chamber for further processing. The substrate can be moved directly from the first chamber to a different processing chamber, or the substrate can be moved from the first chamber to one or more transfer chambers and then moved to a different predetermined processing chamber. Therefore, the processing device can include a connection transfer station Multiple chambers. Such devices are called "cluster tools" or "cluster systems".

Typically, a cluster tool is a modular system that includes multiple chambers that perform various functions, including substrate center finding and positioning, degassing, annealing, deposition, and/or etching. According to one or more embodiments, the cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber houses a robot for transporting the substrate between the processing chamber and the load lock chamber. The transfer chamber is typically maintained in a vacuum condition and provides an intermediate step for the substrate to be transported from one chamber to another and/or to a load lock chamber at the front end of the cluster tool. Two clustering tools known to be suitable for the present invention are Centura® and Endura®, both of which are taken from Applied Materials, Inc., Santa Clara, California. The details of this stepped vacuum substrate processing apparatus are described in U.S. Patent No. entitled "Staged-Vacuum Wafer Processing Apparatus and Method" by Tepman et al., February 16, 1993. No. 5, 186, 718. The exact configuration and combination of chambers can be varied to perform the specific steps of the processes described herein. Other available processing chambers include cyclic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, heat treatment such as RTP, electricity Slurry nitriding, degassing, positioning, hydroxylation and other substrate treatment, but not limited to this. By processing in the chamber of the cluster tool, it is possible to avoid contamination of the surface of the substrate by atmospheric impurities prior to deposition of the subsequent film.

According to one or more embodiments, the substrate is continuously under vacuum or "load lock" conditions and does not contact ambient air as it moves from one chamber to the next. Therefore, the transfer chamber is under vacuum and "pumped back" under vacuum pressure. Dull gas can be stored in the processing chamber or transfer chamber. In some embodiments, the blunt gas is used for purification The gas, after forming a layer on the surface of the substrate, removes some or all of the reactants. In accordance with one or more embodiments, a purge gas is injected at the outlet of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and/or additional processing chambers. Therefore, the blunt airflow will form a curtain at the exit of the chamber.

The substrate can be processed in a single substrate deposition chamber where a single substrate is loaded, processed, and unloaded prior to processing another substrate. The substrate can also be processed in a continuous manner as in a transport system wherein a plurality of substrates are individually loaded into the first portion of the chamber, moved through the chamber, and unloaded from the second portion of the chamber. The shape of the chamber and associated transport system may constitute a straight path or a curved path. In addition, the processing chamber can be a rotating rack in which a plurality of substrates are moved about a central axis and are deposited, etched, annealed, cleaned, etc. throughout the rotating path.

The substrate can be heated or cooled during processing. Heating or cooling may be achieved by any suitable means, including changing the temperature of the substrate support and flowing the heating or cooling gas to the surface of the substrate, but not limited thereto. In some embodiments, the substrate support includes a heater/cooler that is controlled to conduct a change in substrate temperature. In one or more embodiments, the gas used (reactive gas or blunt gas) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater/cooler is disposed within a chamber adjacent the surface of the substrate to convect the substrate temperature.

The substrate may also be fixed or rotated during processing. The substrate can be rotated continuously or in a discontinuous phase. For example, the substrate can be rotated throughout the process, or the substrate can be rotated a small amount between contacting different reactive gases or purge gases. Rotating the substrate during processing (whether continuous or in stages) helps to minimize the effects of local variations such as gas flow geometry, resulting in more uniform deposition or Etching.

In an atomic layer deposition type chamber, the substrate may be contacted with the first and second precursors by spatial or temporal separation. Time ALD is a conventional process in which a first precursor stream enters a chamber and reacts with a surface. The first precursor of the chamber is purged before flowing into the second precursor. In space ALD, the first and second precursors simultaneously flow into the chamber but are spatially separated so that there is an area between the gas streams to prevent precursor mixing. In space ALD, the substrate must move relative to the gas distribution plate and vice versa.

The description of "an embodiment", "an embodiment", "one or more embodiments" or "an embodiment" means that the particular features, structures, materials or characteristics described in the embodiments are included in the specification. At least one embodiment of the invention. Terms such as "in one or more embodiments," "in some embodiments," "in an embodiment," or "in an embodiment" are not necessarily referring to the invention. Example. In addition, in one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

While the invention has been described above in terms of the specific embodiments, it is understood that the embodiments are merely illustrative of the principles and applications of the invention. Those skilled in the art can make various modifications and refinements to the methods and apparatus of the present invention without departing from the spirit and scope of the invention. The invention is intended to cover modifications and variations and equivalents thereof within the scope of the appended claims.

100‧‧‧Microelectronics

105‧‧‧Substrate

110‧‧‧ dielectric layer

115‧‧‧ side wall

120‧‧‧ bottom

150‧‧‧ trench

160‧‧‧ openings

Claims (20)

A method of forming a semiconductor device, the method comprising: a. depositing a film comprising manganese nitride onto a dielectric; b. depositing a copper seed layer onto the film; and c. depositing a copper fill layer to On the copper seed layer. The method of claim 1, wherein the dielectric is a low-k dielectric. The method of claim 1 further comprising depositing a pore sealant onto the dielectric prior to depositing the film comprising manganese nitride. The method of claim 1, wherein depositing a copper seed layer comprises chemical vapor deposition, atomic layer deposition, physical vapor deposition, or electrochemical deposition. The method of claim 1, wherein the manganese nitride is deposited by atomic layer deposition. The method of claim 1, further comprising treating the manganese nitride film with an ammonia plasma post treatment. The method of claim 1, wherein the manganese nitride and the copper seed layer are deposited in the same chamber. The method of claim 1, wherein the manganese nitride has a chemical formula of Mn ₃ N ₂ . A method of forming a semiconductor device, the method comprising: a. depositing a film comprising manganese nitride onto a dielectric; b. depositing a film comprising cobalt or germanium onto the film comprising manganese nitride, or Doping the manganese nitride layer with cobalt or antimony; c. depositing a copper seed layer; and d. depositing a copper fill layer onto the copper seed layer. The method of claim 9, wherein the dielectric is a low-k dielectric. The method of claim 10, further comprising depositing a pore sealant onto the low-k dielectric prior to depositing the film comprising manganese nitride. The method of claim 10, wherein depositing a copper seed layer comprises chemical vapor deposition, atomic layer deposition, physical vapor deposition, or electrochemical deposition. The method of claim 10, wherein the manganese nitride is deposited by atomic layer deposition. The method of claim 10, further comprising treating the manganese nitride film with an ammonia plasma post treatment. The method of claim 10, wherein the manganese nitride and the copper seed layer are Deposited in the same chamber. The method of claim 10, wherein depositing the manganese nitride and depositing the film comprising cobalt or ruthenium is performed without breaking the vacuum. The method of claim 10, wherein the manganese nitride has a chemical formula of Mn ₃ N ₂ . A semiconductor device comprising: a. a low-k dielectric; b. a manganese nitride layer on the low-k dielectric; c. a seed layer, the seed layer selected from a copper seed layer Or electrochemically depositing a seed layer on the manganese nitride layer; d. a copper layer on the copper seed layer. The semiconductor device of claim 18, further comprising a cobalt or germanium containing layer on the manganese nitride layer but below the seed layer. The semiconductor device of claim 18, wherein the seed layer comprises a copper seed layer.