KR20070037492A - System and method for forming multi-component dielectric films - Google Patents

Abstract

The present invention provides a system and method for mixing precursors, whereby a mixture of precursors is present together in a chamber during a single pulse step in an atomic layer deposition (ALD) process, thereby forming a multicomponent film. The precursor consists of at least one different chemical component, which will form a monolayer, thereby making a multicomponent film. In a further aspect of the invention, a dielectric film having a composition gradient is provided.

Description

System and method for forming multicomponent dielectric film {SYSTEM AND METHOD FOR FORMING MULTI-COMPONENT DIELECTRIC FILMS}

Cross Reference of Related Application

This application is a partial, continuous application of US patent application Ser. No. 10 / 829,781, filed April 21, 2004, titled Systems and Methods for Forming Multicomponent Dielectric Films, the entirety of which is incorporated herein by reference.

In general, the present invention relates to systems and methods for forming dielectric films in semiconductor applications. More particularly, the present invention relates to systems and methods for producing multicomponent dielectric films on substrates using mixed evaporation precursors.

At the same time as the intention and complexity towards miniaturization of microelectronics has increased, the number of transistors per integrated circuit has increased dramatically and is growing to meet the demand for faster, smaller and more powerful electronic systems. However, traditional silicon-based transistor geometries are at their peak, in which case the silicon dioxide gate dielectric becomes a slightly thicker primary layer and the tunneling of electrons becomes more prevalent, thereby increasing power dissipation and causing current leakage. Therefore, there is a great need for an alternative dielectric having a higher permittivity or dielectric constant than silicon dioxide and capable of preventing current tunneling or leakage. The most likely dielectric candidates to replace silicon dioxide include hafnium oxide, zirconium oxide, and tantalum oxide.

Unfortunately, these materials, unlike silicon dioxide, are chemically and thermally unstable over silicon, which forms defects and charge traps at the interface between the metal dielectric and the silicon substrate. Charge traps and defects absorb the voltage applied to the gate and disrupt the transistor's performance and reliability. To limit the formation of interfacial charge traps and defects, an interfacial layer of silicon dioxide is deposited between the dielectric and the silicon substrate. The silicon dioxide interface buffers the silicon substrate from the dielectric, and the silicon dioxide interface cannot have compatibility with the surface properties of the dielectric. Thus, there is a need for producing high k dielectrics with very thin interfaces that can improve the chemistry and surface properties of dielectric and silicon substrates while minimizing equivalent physical oxide thickness.

Conventional deposition techniques for making films, such as chemical vapor deposition (CVD), cannot meet the demands of advanced thin films. The CVD process can be tailored to provide conformal films with improved step ranges, and the CVD process requires high process temperatures. For example, one obstacle in making high k gate dielectrics is the formation of interfacial silicon oxide layers during the CVD process. Gas phase reactions in CVD lead to particle generation. Another obstacle is the limitation of prior art CVD processes in depositing ultra thin films for high k gate dielectrics on silicon substrates.

An alternative to traditional CVD processes for deposition is atomic layer deposition (ALD). ALD has several advantages over traditional CVD. ALD can be carried out at relatively low temperatures that are compatible with industry trends towards lower temperatures and can produce conformal thin films. Existing methods for depositing multicomponent films, such as Hf _x Si _y O ₂ (x + y = 1) films using an ALD process, include laminates of HfO ₂ and SiO ₂ films using a sequential vapor deposition method. laminate) to deposit a film. The precursor chemicals are not mixed, instead Hf containing the precursor and Si containing the precursor are sequentially pulsed independently into the chamber thereby forming a laminate layer of HfO ₂ and SiO ₂ separately. No precursor mixing is prohibited and the chamber is cleaned with one precursor before the second precursor is pulsed. Once the laminate film is formed to the required thickness, the film is annealed and leads to a more continuous composition through the film. This approach of stacking different laminate layers leads to a large number of electron traps in the film due to the many interfaces that require high thermal annealing to fix the traps. The addition of a high temperature thermal annealing step increases time and cost for the fabrication of the semiconductor and can result in undesired movement of the elements from the layers already formed on the wafer. In addition, it is difficult to control the stoichiometric composition of the multicomponent film in the lamination method. The dielectric constant (k), crystal temperature and refractive index of the HfSiOx film cannot be easily controlled by one traditional chemical sequential precursor pulse method (such as laminate method). In addition, the cycle time required to form films of the desired thickness using sequential pulses and cleaning of one conventional chemical precursor at a time is unrealistic and requires more time in future IC fabrication.

Attempts to produce multicomponent films using mixed precursors have been limited to traditional CVD methods. For example, US Pat. Nos. 6,537,613 and 6,238,734 (hereinafter '613,' 734) to Senzaki et al. Generate a compositional gradient comprising metal and metalloid compounds by direct liquid injection. Systems and methods for the following are generally disclosed. In direct liquid injection (DLI), the metal and semimetal precursors are mixed with each other to form a solvent-free liquid mixture prior to injection of the mixture into the deposition system.

The methods disclosed in the 613 'and 734' patents have several disadvantages. In particular, the liquid mixture to be injected. If the liquid mixture is not mixed thoroughly, a film with a non-homogeneous composition and slope will form on the substrate. In addition, given the proper volume of sample, there is no guarantee that the mixture will evaporate uniformly because each precursor has a unique boiling point, vapor pressure, and volatility. In addition, if the mismatch in boiling point between the precursors is significant, one precursor may decompose at the boiling point forming the second particulates and contaminants. In general, the precursors did not mix properly and resulted in a non-uniform film composition, or the mixing of the two vapors caused a preliminary reaction in the gas phase resulting in the formation of particles or contaminants deposited on the wafer.

Thus, there is a need for further development in the method of making multicomponent films. Particularly so is the need for a method for producing multicomponent films using ALD processes. This method is required to provide control of the stoichiometric composition or tilt of the multicomponent film.

In general, the inventors have found a method to provide for mixing evaporated precursors, whereby the mixture of evaporated precursors causes the chamber during a single deposition or pulse step in a Wafer Layer Deposition (ALD) process to form a multicomponent film. Exists together in The evaporated precursors each consist of at least one different chemical component and these different components will form a monolayer thereby making a multicomponent film. We call this method "simultaneous injection ALD." This method is different from the prior art and the evaporated precursor is pulsed separately into the chamber in an ALD process thereby forming a separate monolayer containing only one component.

One aspect of the invention provides a system and method for making a multicomponent dielectric film by mixing precursors that have evaporated together and then injecting or co-injecting the vaporized precursors, whereby the mixture of precursors is transferred to an ALD chamber. exist. The term "multicomponent" film as used herein means that the film contains two or more metal or semimetal elements. Various multicomponent films may be formed by the present invention, including but not limited to metals, alloys, mixed metal oxides, silicates, nitrides, oxynitrides, and mixtures thereof.

In one embodiment of the invention, a barrier is provided for forming a thin film on the surface of a substrate by atomic layer deposition, in which each of the precursors contains at least one different chemical component (generally a metal or semimetal element). The vaporized precursors above are transported together into a process chamber thereby forming a monolayer on the surface of the substrate, the monolayer containing each of the separated chemical components. In general, the term simultaneous injection is used to mean that two or more precursors with one or more different chemical components are present in the chamber, whereby the film is produced with multiple components. This can be done by transporting or injecting the precursor together in a vapor or liquid state into the process chamber, or by mixing the precursor within the process chamber. Mixing of the precursors prior to entry into the process chamber is preferred but not necessary.

In another aspect, the present invention provides a system for forming a multicomponent film. In one embodiment, the system generally includes one or more evaporators in which each evaporator is coupled to the manifold. The manifold is configured to mix the evaporated precursor generated by the evaporator. The manifold is coupled to the inlet to the process chamber and the mixed precursor is injected into the chamber through the inlet. In one embodiment, the inlet consists of an injector, such as a showerhead injector. Precursors can be mixed in the injector but not in the manifold.

In another aspect of the present invention, a system and method are provided wherein the process chamber is configured to execute a deposition method on a single substrate. Alternatively, systems and methods are provided, in which case the process chamber is configured to perform the deposition method on a plurality of substrates, typically 1 to 200 substrates. In one example, the batch process chamber contains 1 to 200 substrates, where the substrate is a silicon wafer having a 200 mm diameter. Generally, the process chamber contains about 1 to 150 substrates, where the substrate is a silicon wafer with a diameter of 2000 mm. If the substrate is a silicon wafer with a diameter of 300 mm, it would be common for the process chamber to contain 1 to 100 substrates. Recently, "mini-batch reactors have been developed, in which case a batch of 1 to 50 numbers of substrates is accommodated in the process chamber. In this case the substrates are typically silicon wafers having a diameter of 200 mm or 300 mm. Alternatively, the mini-batch process chamber is configured to process 1 to 25 substrates, the substrate is a typical silicon wafer with a diameter of 200 mm or 300 mm An example of a mini-batch system is the designation of a heat treatment system and a configurable vertical chamber. Is described in PCT Patent Application No. PCT / US03 / 21575, the entirety of which is hereby incorporated by reference.

In another aspect of the invention, systems and methods are provided for forming multicomponent films having compositional gradients. In one embodiment, a method of making a multicomponent film is provided, which is characterized in that two or more evaporated precursors are injected together into a process chamber, each precursor containing at least one different chemical component, thereby Forming a monolayer on the surface, each gas flow rate of the evaporated precursor injected into the chamber is selectively controlled, whereby the desired compositional gradient of one or more different chemical components is formed in the film.

In a further aspect of the invention, a dielectric film having a composition gradient is provided, which comprises a silicon-rich bottom layer, a nitrogen-rich top layer, and one or more hafnium-rich layers between the top and bottom layers. In one embodiment nitrogen is selectively deposited on or near the silicon substrate-dielectric interface, thereby preventing boron diffusion. In a further embodiment, there is provided a system and method for preventing the diffusion of boron, in which case it does not affect the quality of the interface between the silicon and nitride dielectric and the equivalent physical oxide thickness of the dielectric, thereby leading to high trap density. . In one embodiment, the composition gradient can be used to "buffer" the dielectric and the substrate. For example, when the substrate is silicon, the first layer is abundantly deposited with silicon, with little amount of the second deposited metal constituting the dielectric. On top of the first layer, a second layer, which primarily comprises a deposition metal that organizes the dielectric, is deposited with an almost small amount of silicon. In certain embodiments, additional layers may be added to fuse the chemical and surface properties of adjacent layers. In various embodiments, each layer may be in situ oxidized, reduced, nitrided, or a combination thereof.

The present invention also provides a system and method for producing a multicomponent oxynitride film, in which case the multicomponent film is formed by the method described above, after which the film is ozone, oxygen, peroxide, water, It is oxidized at an elevated temperature with an oxidation reactant selected from the group consisting of air, nitros oxides, nitric oxides, N-oxides, and mixtures thereof. A particular advantage is that the oxidation step can be performed in situ. After oxidation, the activated nitrogen source is sequentially transported to the process chamber, allowing reaction with the oxidized layer at elevated temperatures to produce oxynitride.

In a preferred embodiment, the present invention provides a system and method for preparing multicomponent oxynitrides by mixing a precursor containing a nitride reactant into a chamber and by performing an ALD process at a relatively low temperature. Suitable nitriding agents are from the group consisting of ammonia, deuterated ammonia, ¹⁵ N-ammonia, amines or amides, hydrazines, alkyl hydrazines, nitrogen gases, nitric oxides, nitros oxides, nitrogen radicals, N-oxides, and mixtures thereof Can be selected.

Other aspects, embodiments and advantages of the present invention will become apparent upon reading the following detailed description of the invention and the appended claims provided below.

1A is a block schematic diagram of a system for manufacturing a multilayer film, multiple components in accordance with an embodiment of the present invention.

1B is a partial block schematic diagram of an iron chamber in accordance with an alternative embodiment of the present invention.

2 is a cross-sectional view of a high k dielectric gate material formed using the system and method of the present invention.

3 is a flow chart illustrating a method for producing a composition change film according to one embodiment of the present invention.

4 shows the relationship between the deposition precursor gas flow rate and the film composition. In this particular example, the deposition and composition of the hafnium-silicon film can be modified by controlling the hafnium and silicon deposition gas flow rates.

5 tabulates the results of atomic component analysis of various HfSiOx films made by the systems and methods of the present invention. This result indicates that for a given hafnium and silicon content concentration, the ratio of oxygen atoms to hafnium and silicon atoms is about two. This result indicates that, over a specific range, HfSiO films prepared according to the systems and methods of the present invention provide films with the structural formula Hf _x Si _{1 - x} O ₂ . Percentages of carbon, hydrogen and nitrogen are found only in trace amounts.

Figure 6a and 6b illustrate a produced by the systems and methods formula Hf _{0 .5} Si _{0 .5} O film, X-ray photoelectron spectroscopy of the light having the _{2 (x-ray photoelectron spectroscopy,} XPS) spectrum of the present invention. In particular, FIG. 6A brightens the XPS spectrum of the 4f region of hafnium in the film. 6B brightens the XPS spectrum of the 2p region of silicon found in the film. In both spectra, the impurities are very small or absent.

It represents a refractive index of _x O _{2 -} 7 is a Hf / (Hf + Si) of a variety of 50nm thickness above the silicon wafer measured as a function of the ratio Hf _x Si _1. The graph compares the index of refraction for as-deposited films and post-deposition annealed films.

8 is Hf _x Si _{1 -} shows the change of the deposition rate on the _x O _2, which comprises a hafnium ozone for the deposition temperature results from the oxidation of the silicon film.

9A-9C show various TEM cross-sectional images of Hf _0.58 Si _0.42 O ₂ films deposited at 400 ° C. on silicon substrates last treated with HF. Figure 9a, 9b, 9c shows a TEM image of Hf _{0 .58} Si _{0 .42} O ₂ film having a dielectric layer thickness of each of 2.3nm, 4.3nm, 6.5nm. In each case the thickness of the interface is measured at about 1 nm.

10 is a TEM cross-sectional image of Hf _0.58 Si _0.42 O ₂ with a polysilicon cap layer after annealing at 700 ° C. at N ₂ .

11 is different Hf _x Si ₁ on a silicon wafer treated with a final HF _{- x} O measures the leakage current density and the electric capacity due to the thickness of an equivalent amount of hafnium in an amount of _{2 (capacitance equivalent thickness, CET)} .

Figure 12 is to measure the film tensile stress due to the temperature for O ₂ Hf _{0 .34 0 .66} Si film of a thickness of 50nm.

Figure 13 shows the X-ray light electron spectroscopy (XPS) spectra for the nitrogen 1s and hafnium 4p _3/2 for the nitriding the HfSiO _x film with ammonia in the annealing step after deposition. For HfSiO _x , the XPS spectrum of the HfSiON film at the take-off angle (TOA) of the various samples indicates the presence of nitrogen in the film.

14 is a graph of the deposition rate of HfO ₂ resulting from oxidation of hafnium dialkyl amide with ozone, by deposition temperature.

15 is a cross-sectional view of a thin film having a composition gradient formed by the co-injection system and method of the present invention. FIG. 15 shows a sequential and in-situ thin film comprising HfSiO _x , HfO ₂ and HfO _x N _y or HfSiON layers.

16A and 16B show the reaction scheme, which illustrates two different methods of making the metal, alloy or mixed metal oxynitrides of the present invention. 16A shows a relatively hot process for producing oxynitride, with the oxidation step preceding the nitriding step. In FIG. 16B, the oxidation step is reserved until the film is nitrided at a relatively low temperature.

17 shows the composition profile below the surface of a typical oxynitride film. Nitrogen concentration is highest on the surface of the film and gradually decreases below the surface until it reaches the HfO ₂ layer. With further penetration into the film, the concentration of HfO ₂ is reduced for HfSiO _x until it reaches the interfacial layer of the silicon substrate.

18 shows a simplified block diagram of one embodiment of a chemical delivery system of the present invention.

19 is a simplified block diagram of a chemical delivery system according to another embodiment of the present invention.

In general, the inventors have discovered a method of providing a precursor to mix, whereby a mixture of precursors is present in the chamber during one pulse step in an atomic layer deposition process (ALD), thereby providing a single compound with a complex chemical compound on the surface of the substrate. Form a layer. The precursors consist of different chemical compounds and these compounds will form a multicomponent film. The inventor refers to this method as "simultaneous injection ALD." This method is different from the prior art, and the evaporated precursor is separated into the chamber in an ALD process, or is pulsed. Various multicomponent films may be formed by the present invention, including but not limited to metals, alloys, mixed metal oxides, silicates, nitrides, oxynitrides, and mixtures thereof.

In one aspect, the present invention provides a system and method for reproducible and nearly uniform control of the stoichiometric composition of a multicomponent film.

In a series of embodiments, the present invention provides a system and method for producing a dielectric that can prevent leakage or tunneling and that has a higher permittivity or dielectric constant than silicon dioxide. In another aspect of the invention there is provided a system and method for fabricating an interface, which interface can improve the chemical and surface properties of dielectric and silicon substrates and minimize equivalent physical oxide layers.

In one embodiment and aspect of the present invention, the present invention provides a system and method for selectively depositing nitrogen above or near a silicon substrate-dielectric interface, thereby preventing boron diffusion and increasing the crystal temperature of the high k layer. Let's do it. In a further embodiment, there is provided a system and method for preventing boron diffusion, in which case it does not affect the equivalent physical oxide thickness of the dielectric and the quality of the interface between the silicon and nitride dielectrics, thereby, for example, high traps. ) Leads to density.

In a general embodiment of the present invention, there is provided a system and method for performing low temperature nitriding of a film, and in another embodiment of the present invention, the present invention sequentially provides a system and method for delivering an in situ nitrogen reactant. Providing, thereby eliminating the need for an external plasma source and having the benefit of less process steps and time.

In another aspect of the present invention, a system for forming a multicomponent film is provided. In one embodiment shown in FIG. 1A, the system generally includes one or more evaporators, each evaporator coupled to a manifold. The manifold is coupled to the inlet to the reaction or deposition chamber, which consists of an injector such as a showerhead and the like.

Each evaporator carries one deposition precursor that constitutes one or more deposition metals. Each evaporator is connected to a mass flow controller and a temperature control unit. The mass flow controller and temperature unit are selectively controlled to mitigate the concentration of deposition precursors present in the process chamber. In one embodiment, each mass flow controller mitigates the flow of carrier gas through the system, which in turn transports and dilutes the deposition precursor to the manifold or process chamber.

In a series of embodiments, the evaporator is a bubbler, which evaporates one deposition precursor that constitutes at least one deposition metal. The compressed gas comprising the carrier gas is bubbled into the deposition precursor. The flow rate of the compressed gas can be selectively controlled, thereby adjusting the concentration of the deposition precursor present in the process chamber.

In one embodiment, the manifold promotes mixing of the deposition precursor prior to delivery to the process chamber. In one embodiment, the manifold contains a T-junction cavity, which receives and mixes the deposition precursor prior to delivery to the process chamber. The manifold may be heated thereby facilitating the flow of the deposition precursor into the process chamber to prevent condensation in the manifold. Alternatively mixing of the precursor may occur in the process chamber and the manifold may be removed.

The deposition precursor is generally delivered through the gas inlet to the process chamber, and a single layer of the deposition precursor is chemically and / or physically absorbed onto the substrate or surface. The substrate can be silicon, metal, alloy, glass or polymeric, plastic, organic or inorganic work piece. The gas inlet may have various forms. In one example, the gas inlet consists of an injector such as a showerhead injector and the like. Alternatively, the deposition precursor is delivered to the substrate surface by the composite injector.

In general, the substrate is supported on a wafer support such as electrostatic or vacuum chuck during deposition when a single wafer chamber is used. In one embodiment, the chuck may heat or cool the substrate by a conduction, convection, radiation or non-radiation process or a mixture thereof. Alternatively the wafer support may be a boat or cassette, which supports the composite substrate for batch processing as shown in FIG. 1B. Composite substrates generally have a number of 1 to 200 substrates and are preferably 1 to 150 substrates, alternatively 1 to 100 substrates, alternatively 1 to 50 substrates, and optionally 1 to 25 substrates. Has the number of substrates.

The inlet port provides an oxidation, reduction or nitriding reactant into the process chamber switchably in situ, thereby activating sequential oxidation, reduction nitriding of the substrate surface or monolayer.

In another aspect of the present invention, a dielectric film having a compositional gradient is provided, which comprises at least one hafnium rich layer, a nitrogen rich top layer, and a silicon rich bottom layer between the top and bottom layers. In one embodiment, nitrogen is selectively deposited over or near the silicon substrate-dielectric interface thereby preventing boron diffusion. In a further embodiment, a system and method are provided for preventing boron diffusion without affecting the quality of the interface between the silicon and nitride dielectric and the equivalent physical oxide thickness of the dielectric, thereby leading to high trap density.

The present invention also provides a system and method for producing a multicomponent oxynitride film, in which case the multicomponent film is formed by the method described above, after which the film is ozone, oxygen, peroxide, water And is oxidized at elevated temperatures with an oxidant selected from the group consisting of air, nitros oxides, nitric oxides, H ₂ O ₂ , N-oxides, and mixtures thereof. As a particular advantage, the oxidation step can be carried out in situ. Following oxidation, the activated nitrogen particles are sequentially transported to the process chamber and make it possible to react with the oxidized layer to form oxynitride at elevated temperatures. This step is also performed in situ.

The present invention provides a system and method for producing multicomponent oxynitride films by performing an ALD process at relatively low temperatures and mixing precursors containing nitride reactants into the chamber. Suitable nitride elements consist of ammonia, deuterated ammonia, ¹⁵ N-ammonia, amines, amides, hydrazines, alkyl hydrazines, nitrogen gases, nitric oxides, nitros oxides, nitrogen radicals, N oxides, atomic nitrogen, or mixtures thereof It can be selected from the group.

In particular advantage, the multicomponent film of the present invention is formed with compositional gradients. Composition gradients can be used to "buffer" dielectrics and substrates. For example, when the substrate is silicon, the first layer is deposited in abundance of silicon, with little amount of the second deposited metal forming the dielectric. On top of the first layer is deposited a second layer which mainly consists of the deposition metal forming the dielectric, which does not contain silicon. In one embodiment additional layers may be added, thereby mixing the chemical and surface properties of adjacent layers. In various embodiments, each layer may be in situ oxidized, reduced, nitrided, or a combination thereof. The compositional slope provides the refractive index gradient in the film, which provides the film's unique optical properties.

1A is a simplified schematic diagram illustrating one embodiment of a system for making a multicomponent film according to an embodiment of the present invention. Referring to FIG. 1A, system 100 generally includes a process chamber 102, which houses a wafer support 110 for supporting a wafer or substrate 112. Gas inlet 114 is provided for transporting deposition precursors and other gases 103 (e.g., reactant gases such as diluent or oxidizing gases and the like) into chamber 102, thereby over the surface of the substrate. To form various layers or films. In the illustrated embodiment, the gas manifold 104 connects one or more evaporators 107, 109 with the process chamber 102. The illustrated embodiment shows two evaporators, and any number of evaporators may be used. Each evaporator includes a reservoir 116, 118, which individually holds a mixture or deposition precursor of deposition precursors 124, 126, and evaporator elements 120, 122, through which the carrier gas is stored. It is flowed to help evaporate the contents of 116, 118. The flow of carrier gas to the evaporator can be adjusted using a mass flow controller (not shown), thereby controlling the concentration and proportion of the vaporized deposition precursor. Optionally, each evaporator may be provided with a heating element (not shown), thereby facilitating the evaporation of the deposition precursors 124, 126 held in the reservoirs 116, 118. Depending on the physical properties of the deposition precursors 124, 126, a combination and heating of carrier gases may be required thereby evaporating the deposition precursors in the reservoirs 116, 118.

In one embodiment of the invention, a deposition precursor comprising at least one metal is used with the following formula:

M (L) x

Where M is Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy , Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge or its Is a metal selected from the group consisting of mixtures, where L is an amine, amide, alkoxide, halogen, antihydride, alkyl, azide, nitrate, nitrile, cyclopentadienyl, carbonyl, carboxylate, diketonate And a ligand selected from the group consisting of alkyne, alkene, alkyne, or substituted analogs thereof, and combinations thereof, wherein x is an integer equal to or less than the valence for M.

The ligand (L) is advantageously selected equally in each of the deposition precursors, thereby avoiding ligand exchange when each precursor is mixed in evaporated form. Ligand exchange can lead to the formation of particulates, which adversely affects the quality of the deposited film. Ligands which do not undergo ligand exchange in evaporation form are suitable.

In a preferred embodiment, two deposited precursors are selected, the first deposition precursor being hafnium and the second deposition precursor being silicon. The first and second deposition precursors have the same ligand (L), thereby avoiding ligand exchange when the first and second deposition precursors are mixed. Suitable ligands include, but are not limited to, dimethylamine, diethylamine, diethyl methyl amine or tert-butoxide.

The hafnium source may include one or a combination of hafnium dialkyl amides, hafnium alkoxides, hafnium dieketonates, hafnium chloride (HfCl ₄ ), tetrakis (ethylmethylamino) hafnium (TEMA-Hf), and the like. . The silicon source may be one of aminosilane, silicon alkoxide, silicon dialkyl amide, silane, silicon chloride, tetramethyldisilazaene (TMDSO), tetrakis (ethylmethylamino) silicone (TEMA-Si), and the like or Combinations. In a preferred embodiment, the fluid precursors 124, 126 are made up of TEMA-Hf and TEMA Si separately.

Deposition precursors are generally evaporated with an evaporator. Each evaporator holds a single deposition precursor. Each evaporator is connected to a mass flow controller and a heating mechanism. As described in accordance with one embodiment of the present invention, a compositional gradient of one or more chemical components in the deposited film is provided. In one example, selective control of the composition is achieved by controlling the amount of precursor evaporated. The amount of precursor evaporated is generally controlled by adjusting the gas flow controller and / or the temperature unit, where the temperature unit heats the evaporated to evaporate the desired concentration of the selected precursor. Additionally or alternatively, the dilution gas may be transported to the injector 114 or manifold 104 (not shown), and the flow rate of the dilution gas may be selectively controlled and thereby the deposition precursor transported to the chamber 102. Dilute the amount.

The evaporator may consist of a bubbler for evaporating a deposition precursor comprising at least one deposition metal. When the evaporator is a bubbler, a compressed gas, such as a carrier gas, is bubbled into the deposition precursor reservoirs 116, 118. Useful carrier gases include nitrogen, argon, or helium gas. The compressed gas dilutes and transports the deposition precursor into the individual deposition precursor conduits 106 and 108 and facilitates mixing of the deposition precursors. Optionally, to provide compositional gradients in the film, one or more concentrations of the deposition precursor may be functionally controlled by varying the temperature of the bubbler, thereby increasing or decreasing the amount of the deposition precursor that is selectively evaporated. Let's do it. The temperature control can be performed independently or can be performed side by side with the flow rate of the carrier gas and / or with the control of the mass flow controller. Thus, each of the various control mechanisms may be used independently or in various combinations.

In other embodiments, because of the nature of the deposition precursor, the deposition precursor may be volatilized in the reservoirs 107, 109 by photolysis or enzymatic or chemical catalysis.

In other embodiments, precursor reservoirs 116 and 118 may contain a mixture of precursor chemicals. The mixture generally contains at least one metal compound. The ligands of the precursor chemicals are chosen to be the same ligands, whereby there is no change in the chemical properties of the mixture upon ligand exchange. Alternatively, the ligands are chosen such that the chemicals are stable with respect to each other and no ligand exchange occurs. The mixture can then be delivered as a "blended liquid" using Direct Liquid Injection (DLI). A particular advantage of this embodiment is that it allows the formation of materials in a wide range of multicomponent elements, in which case no individual hardware is required to deliver each unique chemical precursor. Examples of materials that can be deposited using the present invention are HfSiO _x , HfSiON, HfSiN, TiALN, TiSiN, TaAlN, TaSiN, HfTiO _x , Ta-Ru alloy, A _x B _y C _z O Including but not limited to elemental metal oxides, quaternary metal nitrides having the formula A _x B _y C _z N, and the like.

In other embodiments, precursor reservoirs 116 and 118 may contain a mixture of precursor chemicals. The mixture generally contains at least one metal compound. The ligands of the precursor chemicals are chosen to be the same ligands, thereby leaving no change in the chemistry of the mixture upon ligand exchange. Alternatively, the ligands are chosen such that the chemicals are stable with respect to each other and no ligand exchange occurs. The mixture can then be delivered as an "aerosol" using known systems, evaporated in a suitable evaporator device and delivered to conduits 106 and 108 as a gas mixture of precursors. In addition, this embodiment allows the formation of materials over a wide range of composite elements, without overlapping the individual hardware required to deliver each unique chemical precursor. Examples of materials that can be deposited using the present invention include HfSiO _x , HfSiON, HfSiN, TiAlN, TiSiN, TaAlN, HfTiO _x , Ta-Ru alloys, quaternary metal oxides such as Formula A _x B _y C _z O, Quaternary metal nitrides such as A _x B _y C _z N and the like, but are not limited thereto.

Referring to FIG. 1A, after the deposition precursors 124, 126 are evaporated, the deposition precursors 124, 126 are transported through the deposition precursor conduits 106, 108 to the manifold 104. Deposition precursor conduits 106 and 108 may be of any shape, size, and length. Conduits 106 and 108 may be insulated or heated, thereby facilitating evaporation. Optionally, conduits 106 and 108 and manifold 104 contain sampling regions for spectroscopically or spectrophotometrically measuring evaporation concentrations and compositions.

Mixing of the precursors can be facilitated by gravity or compressed gas. In addition, mixing may be accomplished by physical means such as a plunger, thereby forcibly injecting the precursors 124, 126 through the conduits 106, 108 into the manifold 104, in this case precursor 124. 126 allows to mix into a homogeneous deposition mixture. In one embodiment, conduits 106 and 108 converge and end at T-junction 130 in manifold 104, in which case precursors 124 and 126 are mixed prior to delivery into process chamber 102.

Alternatively, conduits 106 and 108 may deliver and converge individual precursors directly into the cavity at or near the inlet to the mixing region or chamber 102. In one embodiment, a filter may be inserted and attached to manifold 104, thereby removing unwanted or isolating certain impurities and gases.

Optionally, referring back to the manifold 104 and the conduits 106 and 108, an internally fitted or externally located heating or cooling element may be utilized, thereby minimizing particulate and impurity formation in the film. Discourage mixing.

Manifold 104 may take a variety of forms suitable for mixing the precursor prior to transporting the precursor to chamber 102. Manifold 104 may be a single conduit coupled to an evaporator via a junction, such as T-junction 130. Manifold 104 may include a cavity or reservoir, thereby providing a constant residence time for the precursors to mix. In an alternative embodiment, the manifolds can be completely removed and the deposition precursors are transported directly to the gas inlet 114 and mixed at the gas inlet 114 as they are transported into the chamber 102 (the gas inlet consists of an injector). Same as when).

Referring to FIG. 1A, when precursors 124 and 126 are evaporated, deposition precursors 124 and 126 are transported to chamber 102 through one or more gas inlets 114. The gas inlet may take various forms for delivery of gas to the chamber. In one embodiment, the gas inlet consists of an injector such as a showerhead. It is also within the scope of the present invention to incorporate a showerhead, which provides the desired film using multiple injectors that are adjustable into the process chamber 102. The embodiment shown in FIG. 1A shows a single wafer chamber with one gas inlet 114, and the invention can be employed within a batch process chamber, and can be employed as a mini-batch chamber. This is generally the same as shown in Figure 1B. In a batch or mini-batch chamber, multiple gas inlets 114 are employed and the gas is generally transported across each substrate in a parallel or vertical flow method. An example of a mini-batch chamber is described in PCT Patent No. PCT / US03 / 21575 with the title of the heat treatment system and the configurable vertical chamber, which is the specification adopted herein by reference.

A layer of deposition mixture comprising precursors 124 and 126 is deposited on substrate 112. Suitable substrates include metal, alloy, glass, polymeric, plastic, organic or inorganic workpieces. Depending on the mode of deposition, monolayers or monolayers of the deposition mixture will be formed on the substrate 112. A preferred method for deposition is atomic layer deposition. However, the systems and methods of the present invention can be employed with other deposition techniques.

Referring to FIG. 1A, after deposition of the deposition mixture, excess mixture is flushed from the system through an exhaust port connected to a vacuum pump, which controls system pressure, gas flow and rapid cleaning of the process chamber 102 after each deposition process. To ensure. Wafer support 110 is used to heat and support the substrate during the deposition or annealing step. Wafer supports generally contain heating and cooling elements formed therein. An external heater (not shown) can also be used to control the temperature of the process chamber. Preferably, wafer support 110 is a vacuum or electrostatic chuck.

The process chamber 102 has an inlet 103 that can switchably and sequentially provide other gases used in the cleaning of the chamber or in processing. Reactant gas may be transported into the chamber through the inlet 103. Suitable reactant gases include oxidizing gases, reducing gases, nitriding gases, or mixtures thereof. Other gases that may be transported through the inlet 103 include carriers or inert gases, or mixtures thereof.

In one preferred embodiment, the evaporated deposition precursor is mixed in the manifold prior to introduction into the reaction chamber, thereby providing a more uniform film and allowing maximum control of the composition of the film. Like injectors and the like, each of the evaporated precursors is separated and transportable to the gas inlet, which mixes the gas as they are injected into the chamber, thus eliminating the need for a separate manifold. Various mechanical embodiments are suitable in terms of teaching of the present invention, and the present invention is not limited to any one mechanical configuration. Disclosure of the Invention The present disclosure provides that at least constant mixing of various different precursors may occur, whereby a mixture of precursors having different chemical components is present in the process chamber, thereby forming a composite configuration in one single layer. Form a film with elements.

Reactant gas may enter the process chamber 102 through the inlet 103, whereby it reacts with and / or processes the monolayer comprising the deposition mixture on the surface of the substrate 112. Reactant gas may be supplied to mix directly or into the process chamber 102 or sequentially or simultaneously with the deposition precursor in the gas inlet 114.

Various reactant gases can be used depending on the application. If the reactant gas is an oxidizing gas, the single layer is oxidized. If the reactant gas is a reducing gas, the monolayer is reduced. Similarly, the oxidizing gas may contain ozone, oxygen, singlet oxygen, triplet oxygen, water, peroxide, air, nitrooxide oxide, nitric oxide, H ₂ O ₂ , and mixtures thereof. Include. Suitable reducing gases include hydrogen. Suitable nitriding gases include ammonia, deuterated ammonia, ¹⁵ N-ammonia, hydrazine, alkyl hydrazine, nitrogen dioxide, nitros oxides, nitrogen radicals, nitric oxides, N-oxides, amides, amines, and mixtures thereof. . In another embodiment, after the deposition precursor is deposited over the substrate 112, the substrate 112 is transferred to a second processing unit capable of nitriding, oxidizing, reducing or annealing a single layer over the substrate 112 in vacuum. Can be.

In one example, to form a multicomponent film comprising HfSiN by ALD, hafnium and silicon deposition precursors (e.g., individually TEMA-HF and TEMA-Si) are nitrogen, such as NH ₃ , to form HfSiN. Along the containing source, they are evaporated, mixed and transported together into the process chamber (also referred to as "pulsed"). This process can be performed when the Hf and Si deposition precursors are mixed together into a process chamber, pulsed and then cleaned. This step forms one ALD cycle thereby forming an HfSiN film. In another embodiment, additional pulse and cleaning steps are performed with an oxidant such as ozone in the ALD cycle to form the HfSiON film.

In one example, the ALD process is performed at process temperatures in the range of about 25 to 800 ° C., more generally in the range of about 50 to 600 ° C., and most commonly in the range of about 100 to 500 ° C. The pressure in the process chamber ranges from 0.001 mTorr to 600 Torr, more typically from about 0.01 mTorr to 100 Torr, most typically from about 0.1 mTorr to 10 Torr. When used, the total inert gas flow rate in the process chamber, including the carrier gas in the bubbler, is generally in the range of about 0 to 20,000 sccm, more generally about 0 to 5,000 sccm.

Optionally, after the deposition precursor is deposited over the substrate 112, the substrate 112 is transferred to a second processing unit capable of nitriding, oxidizing, reducing, or annealing a single layer on the substrate 112 in a vacuum. Can be.

2 is a cross-sectional view of the multi-layer gate dielectric of the present invention. The first layer 200 is selected to improve the high mobility (faster transistor speed) and desirable properties of the stable interface to the substrate 112. Suitably, the first layer is a metal silicate or oxide with a high dielectric constant. Preferably, the first layer is a silicon-rich metal silicate. The silicon element in the metal silicate of the first layer reduces the formation of interfacial defects by mitigating the incompatibility between interfacial silicon dioxide residues on the substrate 112 and metal oxides or pure metals. . Metal elements in the metal silicates contribute to improving the dielectric properties of the first layer. Suitable metals, alloys or mixed metal oxides, nitrides, silicates or oxynitrides of the present invention may be formed by Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe , Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh , Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge or mixtures thereof.

One embodiment of the method of the present invention is shown in the flowchart of FIG. 3. This example is shown for illustrative purposes only and is not intended to limit the invention in any way. In an exemplary embodiment, a first precursor evaporator is provided which has a first precursor comprising Hf (step 150). A second precursor evaporator is provided having a second precursor comprising Si (step 152). The substrate or wafer is placed on the chuck in the reaction chamber (step 154), the process chamber is emptied (step 156), and the substrate is heated to a predetermined process temperature (step 158). As mentioned above, the process temperature is preferably about 50 to 800 ° C, more preferably about 100 to 500 ° C. The first and second precursors are evaporated by bubbling gas through the reservoir, thereby forming first and second evaporated precursors (step 160), mixing (step 162), and flowing into the reaction chamber (step 164). The mixed first and second evaporation precursors are directed directly onto the substrate through a gas inlet such as a showerhead or injection nozzle (step 166).

The present invention also provides a multicomponent film or layer having a composition gradient as shown in FIG. 1 and 2, the deposition of the first layer 200 over the silicon substrate 112 takes place in the process chamber 102. In one example, a film of HfSiO is formed, in which case hafnium is evaporated in evaporator 107 and silicon is evaporated in evaporator 109. Hafnium and silicon deposition precursor vapor is passed to manifold 104 by the carrier gas. Within the manifold, the deposition precursor vapor is mixed and delivered to the gas inlet 114 as a deposition mixture. The gas inlet 114 transports the deposition mixture to the process chamber 102 and the deposition mixture contacts the surface of the substrate 112 and is absorbed over the substrate to form a monolayer of the deposition mixture over the substrate 112. After the process chamber 102 is cleaned with inert gas and emptied under vacuum, ozone gas is sequentially pulsed through the inlet 103 into the process chamber 102. The reactant gas saturates the monolayer on the substrate 112 and forms an atomic layer comprising hafnium, silicon, and oxygen, in which case the amount of silicon is higher than hafnium.

4 shows that by varying the flow of the deposition precursors 124, 126, the concentration of silicon relative to hafnium is tailored to make a multicomponent film. 5 shows that the change in silicon or hafnium concentration is largely dominated by the formula Hf _x Si _{1 - x} O ₂ , where x = 0-1.

XPS studies on Hf _x Si _{1 - x} O ₂ films shed light on the bonding arrangement of atoms in the film. 6A shows the XPS spectrum of hafnium in the film. Based on the magnitude of the binding energy and the strength of the absorption bands, hafnium is mainly found in the silicate form. There is almost no amount of impurities such as HfO ₂ in the spectrum. Hafnium silicide morphology is also not observed. Referring to FIG. 6B, the XPS spectrum of silicon indicates that the silicon is primarily present as a silicate with little or no SiO ₂ morphology. XPS results demonstrate the advantages of the present invention. This is the formation of uniform hafnium silicates with or without patches or with inclusions of HfO ₂ or SiO ₂ or hafnium silicides.

Referring now to FIG. 7, the refractive index of the dielectric film of the present invention decreases with increasing silicon content. FIG. 7 shows that heating the film in 900 ° C., N ₂ atmosphere does not cause thermal change.

8 shows that the deposition rate is temperature dependent. The linear growth rate of Hf _x Si _{1 - x} O ₂ increases with temperature. Above 400 ° C., the deposition rate increases substantially as the atomic layer deposition (ALD) process adopts a chemical vapor deposition (CVD) mechanism. Sectional transmission electron microscope (TEM) image of the Hf _{0 .58} Si _{0 .42} O ₂ deposited at 400 ℃ on the last treatment (HF-last) silicon substrate with HF, in varying thickness, similar to the interface to be measured to be about 1nm The layer thickness is shown. 9A, 9B, and 9C have dielectric layer thicknesses of 2.3 nm, 4.3 nm, and 6.5 nm, respectively, and the interface thickness is independent of the dielectric thickness. This suggests that when ozone is used as the oxidizing reagent in the ALD process, oxidation of the interface can occur during the first stage of the manufacture of the film.

Heating to an elevated temperature does not change the amorphous state of the dielectric, but annealing reduces the interfacial oxide layer. 10 shows a TEM image of Hf _{0 .58} Si _{0 .42} O ₂ film after annealing. Comparing the thickness of the interfacial oxide layer with respect to FIG. 9, annealing appears to reduce the interfacial layer by 0.3 nm, which improves the capacitance-voltage (CV) or current-voltage (IV) response of the deposited material. 11 shows that the film is electrically stable against thermal annealing. Capacitive equivalent thickness (CET) and low leakage current density are not degraded by the annealing step.

Stress history of the Hf _{0 .34 0 .66} O ₂ Si film thickness of 50nm (Stress hysteresis) measurement was monitored during the annealing to 900 ℃. As shown in Figure 12, the slope of unchanged during heating shows a very stable difference in thermal expansion between the deposited Hf _{0 .34} Si _{0 .66} O ₂ film and the silicon substrate. At about 700 ° C., the stress is more tensile, which shows a morphological change to microcrystalline state. For an HfO ₂ film (not shown) deposited by ALD from TEMA HF and O3 at 300 ° C. and having a stress increase at about 450 ° C., the increase in film stress transition temperature at Hf _× Si _{1 - x} O ₂ was increased to silicon. It can contribute to the increase in content. Thus, an increase in silicon content increases the temperature, at which temperature the film crystallizes.

Suitable sources of hafnium include hafnium dialkyl amides, hafnium alkoxides, hafnium diketonates or hafnium halides. Suitable sources of silicon include silicon halides, silylcone dialkyl amidos or amines, silicon alkoxy, silanes, disilanes, silozaenes, aminodisilanes and disilicon halides. In general, hafnium and silicon sources are chosen to have a common ligand, thereby avoiding the complexity that arises from ligand exchange. Covalently linked and mixed metals and non-covalently mixed metals disclosed in PCT Patent Application No. PCT / US03 / 22236, referred to herein as molecular layer deposition of thin films with mixed components, which are incorporated herein by reference are precursors for deposition. Can be used as. Non-covalent forms of hydrogen bonds, coordination bonds, metal-metal bonds, metal-π, metal-π ^* , π-π bonds, sigma-sigma bonds, ionic bonds, van der Waals interactions, hydrophobic / hydrophilic interactions, Polar bonding or dipole moment interaction. Sources of inert gas include carrier gases such as argon, nitrogen, inert gases, or mixtures thereof.

Referring again to FIG. 2, a second layer 202 is deposited over the first layer 200, and the second layer 202 has a greater concentration of hafnium than silicon, ie, hafnium> silicon. Higher concentrations of hafnium ensure that the entire make-up of the dielectric acts like a high k hafnium dielectric. The presence of silicon in the second layer 202 creates a gradual stoichiometric transition from the first layer 200, thereby leaving no abrupt compositional interface that can cause electrical leakage and defects between the individual layers. Subsequent oxidation with ozone allows the second layer 202.

In various embodiments of the invention, the third layer 203 is optionally deposited to primarily contain hafnium, ie hafnium >> silicon, the top second layer 202 is a stack of dielectric layers having a compositional gradient ). Oxidation to the oxidation reactant produces mainly hafnium dioxide. Using this approach, uniform films of any slope, thickness, and composition can be produced accurately and controlled.

In another aspect, the third layer 203 can be nitrided with a nitriding reactant. Nitrogen inclusions prevent the diffusion of impurities such as boron through the dielectric and improve the long performance and reliability of the film.

In one embodiment, the third layer 203 may be thermally nitrided in the presence of ammonia gas as a post deposition anneal step. In another embodiment, the third layer 203 may be nitrided using high energy nitrogen particles generated away from the process chamber 102. According to one aspect of the present invention, FIG. 13 shows the XPS spectrum for an exemplary post-annealed film with ammonia. For the HfSiO reference shown in FIG. 13, the presence of a nitrogen peak near 400 eV indicates the synthesis of nitrogen into the HfSiO layer. The tilt angle (TOA) of the various samples detects the presence of HfSiON not only at the surface of the dielectric but also deep within the film.

Optionally, instead of relying on heat to form and anneal the nitride layer, nitriding can be facilitated by light, heat and chemical initiators. For example, in certain embodiments, direct plasma, remote plasma, downstream plasma, ultraviolet photon plasma, or a combination thereof may be used to promote nitriding. Activation energy sources include plasma, light, laser, radical and microwave energy sources and mixtures thereof.

In a separate embodiment, as mentioned above, suitable nitrogen sources are ammonia, deuterated ammonia, ¹⁵ N rich ammonia, amines, amides, nitrogen gases, hydrazines, alkyl hydrazines, nitros oxides, nitrile oxides, nitrogen radicals, N Oxides, or mixtures thereof.

In another embodiment of the present invention, an atmospheric method is provided that relates to nitriding a film, but nitriding a dielectric. FIG. 14 shows the HfO ₂ deposition rate, which arises from the reaction between the hafnium dialkyl amide precursor and ozone, which increases surprisingly with a decrease in reaction temperature. In view of the reactivity of ozone towards hafnium dialkyl amides, HfSiO _x (300) is a substrate precursor 112, as shown in FIG. 14, by evaporating hafnium and silicon in the respective evaporators 107, 109 of FIG. Is deposited on top of it. Ozone is supplied through the inlet 103 into the process chamber 102 containing the substrate 112. Oxidation occurs rapidly at relatively low temperatures as in FIG. 16A, thereby allowing hafnium oxide 302. In order to protect layer 302 from boron diffusion from the gate electrode, an oxynitride layer 304 is preferably atop the metal oxide layer 302.

There are two ways to deposit the oxynitride layer 304. In the first method, as shown in FIG. 16A, the deposition precursor or precursors 124, 126 are evaporated and injected into the process chamber 102, thereby forming a monolayer of the deposition mixture over the substrate 112.

Referring to FIG. 16A, in spite of the low temperature oxidation allowing the oxide layer 302, thermal oxynitration annealing at 800 ° C. with subsequent ammonia may be acceptable but not desirable from a process point of view. Structurally, this high annealing temperature is of great concern. This is the crystallization of the oxide layer 302 leading to possible defects inherent in or in the grain boundaries of the oxide layer 302.

In a preferred embodiment of the present invention, a second method for depositing oxynitride is shown in FIG. 16B. About the Method in FIG. 16A The method in FIG. 16B is a more economical route to oxynitride 304. Since ozone readily reacts with the metal dialkyl amides, the deposition mixture is first deposited on the substrate 112 and subsequently in situ with ammonia. Following the formation of nitride 303 at a relatively low temperature, oxidation to ozone drives to complete the reaction, which allows oxynitride 304.

In one embodiment of the invention, deuterated ammonia or 15N-ammonia is preferred.

17 shows the composition profile below the surface of oxynitride 304. The nitrogen concentration gradually decreases below the surface until it reaches the largest and HfO ₂ layer at the surface of the film. With further penetration into the film, the concentration of HfO ₂ 302 decreases with respect to HfSiO _x 300 up to the interfacial layer of the silicon substrate 112.

In another illustrated example, the first precursor evaporator is provided with a first precursor comprising Hf (TEMA-HF in this example). Also provided is a second precursor evaporator (TEMA-Si in this example) having a second precursor comprising Si. Multiple or “placements” of substrates or wafers (in this example a batch of 50 substrates were tested) are placed above the substrate holder in the process chamber. In this example, the process chamber is part of a vertical furnace system. The process chamber is emptied and the substrate is heated to the predetermined process temperature. As mentioned above, the process temperature is preferably in the range of about 50 to 800, more preferably about 100 to 500 ° C. Preferred temperature for this example was 275 ° C. The first and second precursors are evaporated by bubbling gas through the reservoir to form the first and second evaporated precursors, which are mixed and flowed into the process chamber. The mixed first and second precursors are directed onto the substrate through suitable gas inlets such as injectors. A single layer of the chemical component of all precursors (eg Hf- and Si-compounds) is formed on the surface of the substrate. The excess of mixed first and second precursors is removed by appropriate discharge and then a pulse of ozone is allowed to flow into the processing chamber thereby reacting with a monolayer of mixed first and second precursors on the substrate surface, thereby Form a uniform layer of hafnium silicate (eg Hf _x Si _1-x O ₂ ). As a particular advantage, the present invention does not lead to mixing of HfO ₂ and SiO _{2 in} the layer, but instead forms a uniform layer of all the components. This process is repeated until the desired film thickness is obtained. In this way, the "co-injection" method has been successfully applied to multiple substrates simultaneously. Table 1 below shows the uniformity of thickness, deposition rate and refractive index, for this example a 300 mm silicon wafer was used. The low refractive index of 1.76 for a similar HfO ₂ thickness (n = 1.88) reflects the synthesis of Si into the film. Almost 100% step range was observed with 0.15um thickness and 50: 1 aspect ratio. Table 2 below shows the compositional analysis of the same method used to make a thick film (200 microseconds), which helps to accurately determine the composition. This result represents the expected ratio of hafnium to silicon to oxygen. Compositional analysis was performed by RBS and NRA techniques known in the art.

Table 1

TABLE 2

According to the present invention, multiple layers of HfSiON can be deposited with different thicknesses and nitrogen or oxygen concentrations. Specific examples illustrating the formation of SiO ₂ , HfO ₂ , HfSiO ₂ , HfN, SiN, SiON and HfSiON are shown here, and advanced methods and ALD systems can be adopted to produce any thickness, composition or shape of the thin film. Will be apparent to those skilled in the art, and the thin film is a metal, alloy, or mixed metal oxide, silicate, nitride, oxynitride, or combination thereof.

In another aspect of the invention, alternative chemical delivery systems may be used. 18 illustrates one embodiment of a chemical delivery system of the present invention. Precursors 500 and 501 are stored in a container in a liquid state. The precursor may consist of pure chemicals and may consist of a mixture of one or more chemicals. Precursors 500, 501 are transported directly to liquid injector (DLI) systems 502, 503. DLI systems 502 and 503 control the amount of precursors 500 and 501 delivered to process chamber 506. DLI systems 502 and 503 deliver controlled amounts of precursors 500 and 501 to evaporation chambers 504 and 505. Appropriate DLI systems known in the art may be used. Evaporation chambers 504 and 505 convert precursors 500 and 501 from a liquid state to a gaseous state. Gas is then transported to the chamber 506 and a film is deposited over the substrate 507 which is supported on the substrate support 508. In this schematic, the precursors are mixed before they enter the chamber 506. This is not necessary in the present invention. Each precursor 500, 501 can enter the chamber 506 via separate chemical delivery paths and they will not mix until they are in the chamber.

19 illustrates another embodiment of the chemical delivery system of the present invention. Precursors 600, 601 are held in a container in a liquid state. The precursor may consist of pure chemicals and may consist of a mixture of one or more chemicals. Precursors 600, 601 are transported to aerosol systems 602, 603, which convert the liquid precursors into aerosols. Appropriate aerosol systems known in the art can be used. Aerosol systems 602 and 603 control the amount of precursors 600 and 601 delivered to process chamber 606. Aerosols 602, 603 deliver controlled amounts of precursors 600, 601 to evaporation chambers 604, 605. Evaporation chambers 604, 605 convert precursors 600, 601 from a liquid state to a gaseous state. Gas is then transported to the chamber 606 and a film is deposited over the substrate 607 which is supported on the substrate support 608. In this schematic, the precursors are mixed before they enter the chamber 606. However, this is not necessary in the present invention. Each precursor 600, 601 can enter the chamber 606 via a separate chemical delivery path that will not mix until they are in the chamber.

The previous description of specific embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and many modifications, embodiments and variations may be possible in light of the above disclosure. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (18)

A method for forming a multi-component film on a substrate surface, Injecting a desired amount of two or more precursors into one or more evaporation chambers, each of which contains one or more metal or metalloid components; Evaporating the two or more precursors into the evaporation chamber; Transporting the two or more precursors to a process chamber, wherein the precursors are present together in the process chamber and the process chamber is configured to receive a plurality of substrates; Forming a monolayer on the substrate surface, the monolayer containing each of the metal or semimetal component; And Cleaning the process chamber, A method for forming a multicomponent film on a substrate surface. A method for forming a multicomponent film on a substrate surface, Forming an aerosol from a desired amount of two or more precursors and transporting the aerosol to one or more evaporation chambers, each of which contains one or more metal or semimetal components; Evaporating the two or more precursors into the evaporation chamber; Transporting the two or more precursors to a process chamber, wherein the precursors are present together in the process chamber and the process chamber is configured to receive a plurality of substrates; Forming a monolayer on the substrate surface, the monolayer containing each of the metal or semimetal component; And Cleaning the process chamber, A method for forming a multicomponent film on a substrate surface. The method of claim 1, The precursor has the formula M (L) x, M is Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge and mixtures thereof Is a metal selected from the group of L is an amine, amide, alkoxide, halogen, hydride, alkyl, azide, nitrate, nitrile, cyclopentadienyl, carbonyl, carboxylate, diketonate, alkene, alkyne, substituted analogs thereof (analog ), And combinations thereof, x is an integer equal to or less than the valence number for M, A method for forming a multicomponent film on a substrate surface. The method of claim 2, The precursor has the formula M (L) x, M is Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge and mixtures thereof Is a metal selected from the group of L is an amine, amide, alkoxide, halogen, hydride, alkyl, azide, nitrate, nitrile, cyclopentadienyl, carbonyl, carboxylate, diketonate, alkene, alkyne, substituted analogs thereof, and A ligand selected from the group consisting of combinations thereof, x is an integer equal to or less than the valence for M, A method for forming a multicomponent film on a substrate surface. A system for atomic layer deposition, At least one first evaporator containing a first deposition precursor for deposition; At least one second evaporator containing a second deposition precursor for deposition; A process chamber containing a plurality of substrates in the range of 1 to 200, wherein the process chamber is configured to perform an atomic layer deposition process; And A manifold coupled to the first evaporator and the second evaporator and the process chamber, the manifold configured to mix and transport the first deposition precursor and the second deposition precursor to the process chamber; System for atomic layer deposition. The method of claim 5, The number of the plurality of substrates is 1 to 150, System for atomic layer deposition. The method of claim 5, The number of the plurality of substrates is 1 to 100, System for atomic layer deposition. The method of claim 5, The number of the plurality of substrates is from 1 to 50, System for atomic layer deposition. The method of claim 5, 1 to 25 of the plurality of substrates, System for atomic layer deposition. A system for atomic layer deposition, A first direct liquid injection system configured to inject one or more deposition precursors into the first evaporation chamber; A second direct liquid injection system configured to inject one or more deposition precursors into a second evaporation chamber; And A process chamber coupled to the first evaporation chamber and the second evaporation chamber, the process chamber configured to receive a plurality of substrates and configured to receive the deposition precursor from the evaporation chamber and to perform an atomic layer deposition process. Included, System for atomic layer deposition. A system for atomic layer deposition, A first aerosol system configured to form an aerosol of one or more deposition precursors and to transport the aerosol to a first evaporation chamber; A second aerosol system configured to form an aerosol of one or more deposition precursors and to transport the aerosol to a second evaporation chamber; And A process chamber coupled to the first evaporation chamber and the second evaporation chamber, the process chamber configured to receive a plurality of substrates and configured to receive the deposition precursor from the evaporation chamber and to perform an atomic layer deposition process. Included, System for atomic layer deposition. A method for forming a multicomponent film on a substrate surface, Injecting two or more precursors in a desired amount into one or more evaporation chambers, each of which contains one or more metal or semimetal components; Evaporating the two or more precursors into the evaporation chamber; Transporting the two or more precursors to a process chamber, wherein the precursors are present together in the process chamber and the process chamber is configured to receive one substrate; Forming a monolayer on the substrate surface, the monolayer containing each of the metal or semimetal component; And Cleaning the process chamber, A method for forming a multicomponent film on a substrate surface. A method for forming a multicomponent film on a substrate surface, Forming an aerosol from two or more precursors in a desired amount and transporting the aerosol to one or more evaporation chambers, each of which contains one or more metal or semimetal components; Evaporating the two or more precursors into the evaporation chamber; Transporting the two or more precursors to a process chamber, wherein the precursors are present together in the process chamber and the process chamber is configured to receive one substrate; Forming a monolayer on the substrate surface, the monolayer containing each of the metal or semimetal component; And Cleaning the process chamber, A method for forming a multicomponent film on a substrate surface. The method of claim 12, The precursor has the formula M (L) x, M is Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge and mixtures thereof Is a metal selected from the group of L is an amine, amide, alkoxide, halogen, hydride, alkyl, azide, nitrate, nitrile, cyclopentadienyl, carbonyl, carboxylate, diketonate, alkene, alkyne, substituted analogs thereof, and A ligand selected from the group consisting of combinations thereof, x is an integer equal to or less than the valence for M, A method for forming a multicomponent film on a substrate surface. The method of claim 13, The precursor has the formula M (L) x, M is Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge and mixtures thereof Is a metal selected from the group of L is an amine, amide, alkoxide, halogen, hydride, alkyl, azide, nitrate, nitrile, cyclopentadienyl, carbonyl, carboxylate, diketonate, alkene, alkyne, substituted analogs thereof, and A ligand selected from the group consisting of combinations thereof, x is an integer equal to or less than the valence for M, A method for forming a multicomponent film on a substrate surface. A system for atomic layer deposition, At least a first evaporator containing a first deposition precursor for deposition; At least a second evaporator containing a second deposition precursor for deposition; A process chamber configured to receive one substrate and perform an atomic layer deposition process; And A manifold coupled to the first evaporator and the second evaporator and the process chamber, the manifold configured to mix and transport the first deposition precursor and the second deposition precursor to the process chamber; System for atomic layer deposition. A system for atomic layer deposition, A first direct liquid injection system configured to inject one or more deposition precursors into the first evaporation chamber; A second direct liquid injection system configured to inject one or more deposition precursors into a second evaporation chamber; And A process chamber coupled to the first evaporation chamber and the second evaporation chamber, the process chamber configured to receive a substrate and configured to receive the deposition precursor from the evaporation chamber and to perform an atomic layer deposition process. Included, System for atomic layer deposition. A system for atomic layer deposition, A first aerosol system configured to form an aerosol of one or more deposition precursors and to transport the aerosol to a first evaporation chamber; A second aerosol system configured to form an aerosol of one or more deposition precursors and to transport the aerosol to a second evaporation chamber; And A process chamber coupled to the first evaporation chamber and the second evaporation chamber, the process chamber configured to receive a substrate and configured to receive the deposition precursor from the evaporation chambers and to perform an atomic layer deposition process Including, System for atomic layer deposition.

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