TW201615879A - High temperature silicon oxide atomic layer deposition technology - Google Patents

Abstract

Processes for depositing SiO2 films on a wafer surface utilizing an aminosilane compound as a silicon precursor are described.

Description

High temperature cerium oxide atomic layer deposition technology [Reciprocal Reference of Related Applications]

This application claims priority to U.S. Provisional Application Serial No. 62/059,615, filed on Jan.

Embodiments of the present disclosure generally relate to depositing a SiO ₂ film by atomic layer deposition (ALD). More particularly, the present disclosure relates to a process for forming a highly stable SiO ₂ film on a germanium wafer using an aminodecane compound as a hafnium precursor.

As the size of semiconductor components shrinks, the semiconductor industry's tolerance for process variations continues to decrease. To meet these more stringent process requirements, the industry has developed many new processes that meet the demand for this rigorous process window, but these processes often take longer to complete. For example, for a surface having a high aspect ratio feature of 65 nanometers or less, an ALD process may be required to form a shaped layer that conforms to the shape. ALD is a variant of CVD that exhibits superior step coverage compared to CVD. ALD is based on atomic layer epitaxial growth (ALE), which was originally applied to the manufacture of electroluminescent displays. ALD applies chemical adsorption to deposit a saturated monolayer of reactive precursor molecules on the surface of the substrate.

More than one monolayer of film can be achieved by cyclically pulsing a suitable reaction precursor to the deposition chamber. Each exposure of the deposition surface to the reaction precursor can be spatially and/or temporarily separated by inert gas cleaning and/or vacuum. Subsequent exposure of the surface to the ALD precursor and reactants can add a new atomic layer to the previously deposited layer to form a uniform layer of material on the surface of the substrate. The cycle of the reaction precursor(s) with the inert cleaning gas(s) is repeated to form a layer of material having the desired thickness.

The formation of a high quality, stable SiO ₂ dielectric layer has involved the thermal reaction of the ruthenium directly using the substrate and the CVD deposition using various precursors such as decane or dichloromethane and oxygen sources such as N ₂ O or O ₂ . , or the reaction of tetraethoxy decane (TEOS). These thermal and CVD deposition tendencies require higher temperatures, which are not necessarily suitable for deposition on substrates that have been previously processed or have undergone back-end-of-line (BEOL) processes. Films having a small thickness are also difficult to manufacture by these methods.

In addition, very few germanium associated with ALD precursors are stable at temperatures used in high temperature (>650C) deposition processes. Precursors tend to decompose at high temperatures rather than forming self-limiting monolayers, resulting in poor film quality. Thus, there is a thin, high quality, stable SiO ₂ dielectric that is useful in processes and precursors to form better than those typically used for thermal or CVD film growth. This will be advantageous as a result of the layer.

One or more embodiments of the present disclosure are directed to methods of depositing a film. A wafer with a surface is placed in the reaction chamber. The wafer is heated to a predetermined temperature within the reaction chamber. At least a portion of the wafer is exposed to the tantalum precursor for a predetermined period of time to form a tantalum layer on the wafer. The ruthenium precursor comprises a compound having the general formula R ₃ Si:NY ₃ wherein each R series is independently selected from the group consisting of hydrogen, a halogen selected from the group consisting of Cl, Br and I, a linear or branched C1 a C10 alkyl group, a linear or branched C1-C10 alkoxy group and a C6-C10 aryl group, and each Y group is independently hydrogen, a halogen selected from the group consisting of Cl, Br and I, straight A chain or branched C1-C10 alkyl group, a linear or branched C1-C10 alkyl fluorenyl group and/or a C6-C10 aryl group. At least a portion of the surface of the wafer is exposed to an oxygen plasma and/or oxygen source gas to react with the ruthenium layer on the wafer to form a ruthenium oxide film.

Additional embodiments of the present disclosure are directed to methods of depositing a SiO ₂ film onto a wafer. The wafer surface is exposed to a hafnium precursor, wherein the hafnium precursor comprises R ₃ Si:NY ₃ , wherein each R is individually selected from the group consisting of hydrogen, a halogen selected from the group consisting of Cl, Br, and I, and a linear chain Or branched C1-C10 alkyl, linear or branched C1-C10 alkoxy and/or C6-C10 aryl, and each Y is independently selected from hydrogen, selected from Cl, Br, and a halogen, linear or branched C1-C10 alkyl group, a linear or branched C1-C10 alkyl fluorenyl group and/or a C6-C10 aryl group of the group consisting of I, and wherein the ruthenium precursor At least a portion is absorbed onto the surface of the wafer. The wafer surface is heated to a temperature in the range of from about 450 ° C to about 650 ° C such that the absorbed ruthenium precursor is decomposed on the surface of the wafer to form a single or sub-monolayer ruthenium film. Single or sub-monolayer films and wafer surfaces are exposed to sources of oxygen. The source of oxygen reacts with a single or sub-monolayer ruthenium film to form a single or sub-monolayer SiO ₂ film.

A further embodiment of the present disclosure is directed to a method of forming a highly stable SiO ₂ film on a germanium wafer by ALD. At least one germanium wafer is placed into the susceptor within the reaction chamber. At least one of the tantalum wafers is heated to a temperature in the range of from about 450 °C to about 650 °C. A continuous stream of the ruthenium precursor is introduced into the reaction chamber through a showerhead. The ruthenium precursor comprises R ₃ Si:NY ₃ , wherein each R is independently selected from the group consisting of hydrogen, a halogen, a linear or branched C1-C10 alkyl group selected from the group consisting of Cl, Br and I, a linear or branched C1-C10 alkoxy group and/or a C6-C10 aryl group, and each Y group is independently selected from the group consisting of hydrogen, a halogen selected from the group consisting of Cl, Br, and I, and a linear chain. Or branched C1-C10 alkyl, linear or branched C1-C10 alkyl fluorenyl and/or C6-C10 aryl. An oxygen plasma and/or an oxygen source gas is provided in at least one processing zone of the reaction chamber. The susceptor is rotated such that at least one of the ruthenium wafer passes under the showerhead. At least a portion of the ruthenium precursor is absorbed into the surface of the ruthenium wafer. The oxygen plasma and/or oxygen source gas reacts with the absorbed ruthenium precursor to form a SiO ₂ film.

3

17

30‧‧‧Syringe assembly/gas distribution assembly

40‧‧‧Air curtain

60‧‧‧Substrate/Wafer

66‧‧‧Base

80‧‧‧First Processing Station

82‧‧‧Load lock

84‧‧‧ area

85‧‧‧Second processing station

100‧‧‧Processing chamber/system

110‧‧‧ substrate surface

115‧‧‧ surface

118‧‧‧Surface features

120‧‧‧ single layer

125‧‧‧Sedimentary layer/SiO ₂ layer/SiO ₂ single layer

130‧‧‧Si precursor

135‧‧‧SiO ₂

140‧‧‧Oxygen source

145‧‧‧ products

210

220

230

240

250

260

270

280

425‧‧‧ gas 埠

435‧‧‧ gas 埠

445‧‧‧ gas 埠

455‧‧‧vacuum

In order to enable the above-described features of the present disclosure to be understood in detail, a more specific description of the present disclosure can be obtained by referring to the embodiments (some embodiments are depicted in the accompanying drawings). The simple summary above). However, it should be noted that the accompanying drawings depict only the general embodiments of this disclosure and are not considered The scope of the disclosure is to be construed as being limited by the appended claims.

1A-1H depicts an exemplary ALD deposition cycle for depositing SiO ₂ ; FIG. 2 depicts a flow diagram of an exemplary embodiment of a conformal SiO ₂ layer ALD deposition process; and FIG. 3 depicts a conformal SiO ₂ layer deposited by ALD Example embodiment; FIG. 4 is a schematic plan view of a substrate processing system according to one or more embodiments of the present disclosure, the substrate processing system is configured with four gas distribution component units and a loading station; An outline plan view of a substrate processing system configured with three gas distribution component units; and FIG. 6 depicts an exemplary embodiment of a circular gas distribution assembly.

Before the several exemplary embodiments of the present disclosure are described, it is to be understood that the disclosure is not limited to the details of the structure or process steps mentioned in the following embodiments. The disclosure may have other embodiments and may be embodied or carried out in various ways.

References to "an embodiment", "an embodiment", "a" or "an embodiment" or "an embodiment" or "an embodiment" The structure, material or properties may be included in at least one embodiment of the present disclosure. What's more, throughout the specification, such as "one or more implementations The appearances of the words "in a particular embodiment", "in an embodiment" or "in an embodiment" are not necessarily in the In addition, the particular features, structures, materials, or properties described may be combined in any suitable manner in one or more embodiments.

As used herein, the term "conformal" relates to a layer that adheres to and uniformly covers an exposed surface with a thickness having a change of less than 1% relative to the average thickness of the film. For example, a 1000 Å thick film will have a thickness variation of less than 10 Å. This thickness and variation includes the edges, corners, sides, and bottom of the depression. For example, a conformal layer deposited by ALD in various embodiments of the present disclosure will provide a substantially uniform thickness over the deposited area over a complex surface.

As used herein, the term "continuous" is used to cover all exposed surfaces without the layer of gaps or spots of material exposed beneath the deposited layer. The continuous layer may have a gap or point of exposure that is less than about 1% of the total surface area of the film. The terms "substrate" and "wafer" are used interchangeably when used in the context of the specification and the accompanying claims, all of which are directed to a sheet material having a portion of a process that acts on a surface or surface. It will also be apparent to those skilled in the art that, unless explicitly and conversely stated in the context, reference to a substrate may refer to only a portion of the substrate. For example, as explained in relation to Figure 4, in spatially separated ALD, each precursor is delivered to the substrate, but at any given time, any individual precursor stream is delivered to only a portion of the substrate. In addition, reference to deposition on a substrate may mean A bare substrate and a substrate having one or more films or features deposited on or formed on the substrate.

In one or more embodiments, the Si precursor can be delivered to two or more deposition or processing regions within the processing chamber. In one or more embodiments, the oxygen plasma and/or oxygen source gas can be delivered to two or more processing regions that are different from the Si precursor deposition region. In various embodiments, the deposition regions may alternate spatially with the processing regions such that the wafers may sequentially pass through the deposition regions and then the processing regions.

As used herein, "substrate surface" with respect to the exposed surface of any substrate or the surface of the material formed on the substrate, the film processing is performed on the surface of the substrate during the manufacturing process. For example, depending on the application, the surface of the substrate that can be processed thereon includes, for example, tantalum, niobium oxide, strain tantalum, silicon germanium (SOI), carbon doped germanium oxide, tantalum nitride, tantalum carbide, doped germanium, Materials such as germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal carbides, metal alloys, and other conductive materials. The substrate includes, but is not limited to, semiconductor and insulating wafers that may or may not be further processed to produce electronic and/or optoelectronic components. The substrate can be exposed to a pretreatment process to clean, polish, etch, reduce, oxidize, hydroxylate, anneal, and/or bake the substrate surface. In addition to direct film processing on the surface of the substrate itself, in the embodiments of the present disclosure, any of the disclosed film processing steps can also be practiced on a substrate formed on a substrate, as disclosed in more detail below. And, hereinafter, it is pointed out, for example, that when a via is passed through a thin semiconductor and/or insulating layer on an SOI wafer, the term "substrate surface" is intended to encompass the underlayer(s).

The substrate for use with embodiments of the present disclosure can be any suitable substrate. In some embodiments, the substrate is a strong, separate, substantially planar substrate. When used in the context of this specification and the accompanying claims, the word "separated" when referring to a substrate means that the substrate has a fixed size. A substrate-based semiconductor substrate of one or more embodiments, such as a germanium substrate of 200 mm or 300 mm diameter. In some embodiments, the substrate is one or more of tantalum, niobium, gallium arsenide, gallium nitride, tantalum, gallium phosphide, indium phosphide, sapphire, and tantalum carbide.

The principles and embodiments of the present disclosure relate to the deposition of a SiO ₂ film on the surface of a substrate using an aminodecane precursor that reacts with oxygen.

In various embodiments, the SiO ₂ deposition is performed in a substrate processing system including an ALD injector assembly that is positioned over the surface of the pedestal assembly and/or wafer and aligned with the pedestal assembly and/or wafer surface For continuous deposition to maximize output and improve processing efficiency and uniformity. The substrate processing system can also be configured and used for pre-deposition and post-deposition substrate processing.

Embodiments of the present disclosure are also directed to methods for improving the quality and uniformity of SiO ₂ films in ALD precursors.

Embodiments of the present disclosure also include a showerhead that is spaced from the susceptor assembly/wafer in a vertical orientation.

The terms "reactive gas", "precursor", "reactant" and the like are used interchangeably to mean a gas containing a species, which is used in the context of the specification and the accompanying claims. Reacts in the atomic layer deposition process. For example, the first "reaction gas" can be simple It is absorbed on the surface of the substrate and can be obtained by further chemical reaction with the second reaction gas.

The deposition of the SiO ₂ film can be carried out in a processing chamber in accordance with one or more embodiments of the present disclosure. The processing chamber is generally a sealable outer casing that is sealed under vacuum or at least under low pressure conditions. The system includes a gas distribution assembly that distributes one or more gases throughout the top surface of the substrate. The output face of the gas distribution assembly faces the top surface of the substrate.

The gas distribution assembly may include a plurality of gas crucibles and a plurality of vacuum crucibles for guiding one or more gas streams at the substrate, and a plurality of vacuum crucibles disposed between each gas crucible to pass the gas Transfer out of the processing chamber. In an embodiment, the gas distribution assembly includes a first precursor injector, a second precursor injector, and a cleaning gas injector between the first precursor injector and the second precursor injector. The precursor injector is continuously (or pulsed) flowing into the processing chamber through a plurality of gas helium injections of the reaction precursor of Compound A. The precursor injector is continuously (or pulsed) of the reaction precursor of compound B injected into the processing chamber through a plurality of gas helium. The cleaning gas injector flows into the processing chamber through a continuous (or pulse) of a plurality of gases, non-reactive or cleaning gases. The cleaning gas removes the reactive material and reaction sub-products from the processing chamber. The purge gas system is typically an inert gas such as nitrogen, argon and helium. A gas lanthanum is disposed between the gas enthalpy and the gas enthalpy to separate the precursor of the compound A and the precursor of the compound B, thereby avoiding cross-contamination between the precursors.

In various embodiments, the gas helium may be a showerhead that spreads gas over the area.

Aspects of the disclosure relate to a method of depositing a film on a surface of a substrate, wherein the substrate is heated to a predetermined temperature. Heating the wafer or substrate surface to a predetermined temperature can be performed within the reaction chamber, wherein the wafer can be heated by suitable means (for example, a heat lamp, or resistive heating of the susceptor).

One or more precursor gases may be heated using a resistive heating element.

The gas distribution assembly can provide a continuous flow of the ruthenium precursor to the reaction chamber, wherein the ruthenium precursor stream enters at least one deposition zone and contacts at least a portion of the surface of the heated wafer (or impinges on the surface of the heated wafer) At least a portion of the above) for a predetermined period of time.

The surface of the substrate can be exposed to the oxygen plasma and/or oxygen source gas in at least one of the processing chambers. Exposing at least a portion of the surface of the substrate surface to an oxygen plasma and/or an oxygen source gas comprising ozone, wherein the tantalum precursor is impinged on the surface of the substrate, wherein the oxygen plasma and/or ozone and the surface of the heated wafer At least a portion of the upper ruthenium precursor reacts. In various embodiments, the ozone may comprise an oxygen source gas in the range of 10% to 20%, or an oxygen source gas in the range of 15% to 18%, or a 15% oxygen source gas, or an 18% oxygen source. gas.

In another aspect, a remote plasma source (not shown) can be coupled to the precursor injector and the precursor injector prior to injecting the precursor into the processing chamber. The plasma of the reactive oxygen species can be produced by applying an electric field to the compound in the remote plasma source. Any power source that activates the predetermined compound can be used. For example, power sources using DC, radio frequency (RF), and microwave (MW) based discharge techniques can be used. If an RF power source is used, it can be Any of capacitive coupling or inductive coupling. Activation can also be produced by thermal energy based techniques, gas decomposition techniques, high energy light sources (eg, UV energy), or exposure to x-ray sources. Exemplary remote plasma sources are available from vendors such as MKS Instruments and Advanced Energy Industries.

1A-1H depicts an exemplary ALD deposition cycle for depositing SiO ₂ .

FIG. 1A depicts a wafer or substrate 110 having at least one surface 115 to which a surface 115 can be exposed to precursor molecules. In various embodiments, the hafnium precursor molecules can be gaseous and directed toward the exposed surface 115 of the substrate 110 by a gas distribution component.

In various embodiments, a wafer or substrate can be placed in a susceptor that supports the substrate and transports the substrate between processing locations within the processing chamber. The pedestal can have a recess to receive the substrate and properly position the substrate as it moves. The susceptor can be heated such that the substrate can be heated to a predetermined temperature for processing.

In one or more embodiments, the substrate may be a substrate of a semiconductor material, wherein the semiconductor material may be germanium, strained germanium, germanium on insulator (SOI), tantalum carbide, carbon doped germanium, tantalum nitride, tantalum or arsenic. gallium. In various embodiments, the substrate is a wafer.

FIG. 1B depicts a precursor of gas directed toward the exposed surface 115 of the substrate 110. In various embodiments, the exposed surface 115 can be referred to as the top surface of the substrate, particularly when the gas distribution component is positioned over the base and the substrate, and the precursor is directed downward toward the surface. Conversely, if the gas distribution component is below the susceptor and the gas flow is directed upwards, the exposed surface will be the bottom surface.

In one or more embodiments, the wafer may be a germanium wafer supported by a rotating pedestal such that the surface of the wafer is exposed to the ruthenium precursor for a predetermined amount of time by passing under the showerhead. . In various embodiments, the wafer surface is exposed to the ruthenium precursor by passing the ruthenium precursor through a showerhead and passing the wafer under the showerhead.

In one or more embodiments, the gas precursor 130 can be directed toward the surface 115 of the substrate 110 by individual gas enthalpies of the gas distribution assembly. In various embodiments, the gas precursor 130 can be a cerium (Si) precursor of a gas that is delivered to the reaction chamber in a continuous stream or in a pulsed manner. The continuous stream of Si precursor can enter at least one deposition zone, wherein the deposition zone is a portion of the reaction chamber, and in a portion of the reaction chamber, the gas precursor 130 can be passed through one or more curtains of the cleaning gas and / or limited by one or more vacuum enthalpy that is introduced into the reaction gas (multiple gases). In various embodiments, the Si precursor contacts at least a portion of the surface of the heated wafer for a predetermined period of time. In other words, the substrate surface can be exposed to the Si precursor.

In one or more embodiments, the amount of Si precursor absorbed into the surface of the substrate can be controlled by adjusting the partial pressure of the Si precursor and/or the amount of time the substrate surface is exposed to the Si precursor of the gas. . Lower partial pressures and/or shorter exposure times may be used to create sub-monolayer coverage, or higher partial pressures and/or longer exposure times may be used to produce saturation (ie, single Layer) coverage. Those who are familiar with the technology will The solution is unlikely to achieve 100% surface coverage, and the single layer coverage is intended to contain some obstructions, steps or other physical and/or chemical surface features that may interfere with the space in which the precursor can interfere with the surface site, possibly leaving some Saturated surface coverage of open joint locations.

In various embodiments, the precursor 130 is conformally absorbed into the substrate surface 115.

In one or more embodiments, the Si precursor can be an absorbable surface that can be absorbed into the substrate and deposit a layer of cerium (Si) and/or SiO ₂ to the amino decane compound on surface 115.

In one or more embodiments, the amino decane compound has the formula R ₃ Si:NY ₃ , wherein each R system is independently hydrogen, a halogen selected from the group consisting of Cl, Br, and I, linear Or a branched C ₁ -C ₁₀ alkyl group, a linear or branched C ₁ -C ₁₀ alkoxy group and a C ₆ -C ₁₀ aryl group, and each Y may be independently hydrogen, selected from the group consisting of Cl, Br, and I of the group consisting of halogen, linear or branched C ₁ -C ₁₀ alkyl chain, linear or branched C ₁ -C ₁₀ alkoxy silicon based and / or C ₆ -C ₁₀ aryl base.

In one or more embodiments, each R can be a methyl group (-CH ₃ ), and one or two of Ys can be a linear or branched C ₁ -C ₁₀ alkyl group such that the amino decane compound There is a primary or secondary amine having the formula R ₃ Si:L, wherein each L has a nitrogen bonded to a hydrazine.

In one or more embodiments, the amino decane compound may be selected from the group consisting of N,N-dimethyltrimethylsilylamine (also known as (dimethylamine) trimethyl decane). ((dimethylamine)trimethylsilane)), N,N-diethyltrimethylsilylamine (also known as (diethylamine) trimethylsilane), N- N-methyl-1-(trimethylsilyl)methanamine (also known as (methylamine) trimethylsilane) and N-ethyl N-ethyl-1-(trimethylsilyl)methanamine (also known as (methylamine) trimethylsilane). In various embodiments, the amino decane can also be, for example, NN-diethyl-1,1-dimethylsilylamine or allyl (II) Ethylamine) allyl (diethylamino) dimethylsilane.

In one or more embodiments, the ruthenium precursor can be a compound having the general formula Me ₃ Si:L, wherein Me is a methyl group (-CH ₃ ) and L is a first or second amine, and the crystal The predetermined temperature of the circle is in the range of from about 400 °C to about 700 °C. In various embodiments, the ruthenium precursor can be a compound having the formula Me ₃ Si:L, wherein Me is methyl (-CH ₃ ) and L is a first or second amine, and the wafer is predetermined The temperature is in the range of from about 450 °C to about 650 °C.

In one or more embodiments, each R may be a halogen selected from the group consisting of Cl, Br, and I, and one or two of Ys may be linear or branched C ₁ -C ₁₀ The alkyl group is such that the aminodecane compound has the formula R ₃ Si:L, wherein each L group has a primary or secondary amine with a nitrogen bonded to the hydrazine.

In one or more embodiments, the amino decane compound may be selected from N-methyl-N-trichlorosilylmethanamine (also known as N-(trichloropurine) dimethyl A group consisting of N-(trichlorosilyl)dimethylamine).

In one or more embodiments, the ruthenium precursor can be a compound having the general formula X ₃ Si:L, wherein X is a halogen selected from the group consisting of Cl, Br, I, and a combination of Cl, Br, and I. L is a first stage amine or a second stage amine, and the predetermined temperature of the wafer is in the range of from about 50 °C to about 700 °C. In various embodiments, the ruthenium precursor may be a compound having the general formula X ₃ Si:L, wherein X is a halogen selected from the group consisting of Cl, Br, I, and a combination of Cl, Br, and I, and L is The first primary amine or the second amine, and the predetermined temperature of the wafer is in the range of from about 80 °C to about 450 °C.

In various embodiments, the ruthenium precursor can be heated to a temperature in the range of from about 20 °C to about 200 °C to provide a continuous stream of ruthenium precursor as a vapor to the reaction chamber.

FIG. 1C depicts a single or sub-monolayer 120 of the precursor that is absorbed into the exposed surface 115 of the substrate 110. In various embodiments, The precursor 130 can be drawn into the surface by chemical absorption or physical absorption. In ALD, the precursor 130 can be bonded to the surface site in a self-limiting manner, wherein once the surface becomes full of precursor molecules, the additional precursor molecules do not adhere to the surface, such that all or at least a major portion of the surface location is Precursor occupied.

In one or more embodiments, the substrate can be heated to a predetermined temperature for the precursor reaction. In various embodiments, the substrate can be heated to from about 50 ° C to about 1000 ° C, or from about 80 ° C to about 900 ° C, or from about 200 ° C to about 800 ° C, or from about 300 ° C to about 750 ° C, or about 400 ° C. To a temperature in the range of about 700 ° C, or from about 450 ° C to about 650 ° C. In an embodiment, the substrate can be heated to a predetermined temperature of about 550 °C.

Excess gas precursor that is not absorbed on the substrate surface 115 can be removed by vacuum and/or by cleaning with a non-reactive gas.

Figure 1D depicts the absorbed layer exposed to the reactants to form a layer of SiO ₂ precursor. In one or more embodiments, the surface of the substrate or the Si precursor 130 absorbed on the surface of the substrate is exposed to a reactant reactive with Si to produce a layer of SiO ₂ . In some embodiments, the reactants can be an oxygen source 140. In one or more embodiments, the oxygen source 140 can be an oxygen plasma and/or a gas including ozone. In various embodiments, the oxygen source gas including ozone may also include oxygen (O ₂ ) of the molecule and nitrogen (N ₂ ) of the molecule. In various embodiments, the oxygen plasma can be produced from a combination of O ₂ gas, or O _{2 ,} with a gas selected from the group consisting of He, Ar, Ne, Kr, and He, Ar, Ne, Kr.

In one or more embodiments, the oxygen plasma can be produced as a remote plasma and the plasma species are delivered to the processing chamber to contact the substrate surface.

In one or more embodiments, the source of oxygen includes oxygen plasma and/or ozone. In various embodiments, the ratio of ozone to deposited Si may be 1 to 1, or 2 to 1 or > 2 to 1. The ratio of 1:1 means that the ruthenium precursor has the same exposure time as ozone. A 2:1 ratio means that the ozone exposure time is twice as long as the strontium precursor. In a spatial ALD process, a 2:1 ratio means that the deposited film is more oxidized because the ozone treatment of the film is longer.

In various embodiments, the oxygen source 140 contacts the surface 115 of the substrate that was previously covered with a sub-monolayer or monolayer 120 of Si precursor, wherein the substrate 110 and the absorbed Si precursor 130 may be at a predetermined temperature. In various embodiments, the predetermined temperature may range from about 400 °C to about 700 °C, or from about 450 °C to about 650 °C, or from about 80 °C to about 450 °C.

In various embodiments, the oxygen source 140 comprises substantially no H ₂ O, wherein substantially no H ₂ O means that no H ₂ O is deliberately added to the oxygen source, although a small amount of H ₂ O may be due to absorption or as a source of oxygen. The material is slightly contaminated and exists.

FIG. 1E depicts a sub-monolayer or monolayer 120 of Si precursor that interacts with oxygen source 140 on surface 115 of substrate 110. In various embodiments, when in the case of plasma or oxygen ions and particles, the oxygen source 140 can be directly reacted with the absorbed Si precursor, or the oxygen source gas can be absorbed to the absorbed Si precursor. 120 monolayers or monolayer and reacted, to produce a SiO ₂ film layer.

Figure 1F depicts the reaction secondary product released from the surface of the substrate. The secondary product can be evacuated from the reaction chamber by vacuum. In one or more embodiments, the organic portion and/or the halogen portion of the aminodecane can be separated from the oxime to form a volatile reaction product 145, and the reaction secondary product 145 is released from the surface 115 of the substrate, leaving SiO ₂ Deposited layer 125 of 135.

FIG. 1G depicts an example of repeated exposure, it is now deposited on the surface 115 of the substrate 110 of the SiO ₂ layer 125 is exposed to a Si precursor repeat another cycle 130. The gas Si precursor 130 exposing the exposed surface of the SiO ₂ layer 125 to another agent can form a single or sub-monolayer film 120 of the Si precursor 130 on the previously deposited SiO ₂ 135.

The 1H plot depicts an example absorption that absorbs the monolayer film 120 of the gas Si precursor 130 onto the deposited SiO ₂ monolayer 125. In a similar manner, the absorbed Si precursor monolayer 120 can be subsequently exposed to another cycle of the oxygen source 140. This order can be repeated until a predetermined thickness of SiO ₂ film is deposited on the substrate 110.

In one or more embodiments, the SiO ₂ film is conformally formed on the feature of the component. In some embodiments, the features comprise substantially no carbon or nitrogen contaminants. When used in this respect, substantially non-contaminating means that less than about 2 atomic percent of carbon or nitrogen is present in the feature. The sample SiO ₂ film was grown by thermal oxidation and ALD. As shown in Table 1 below, the amounts of carbon (C) and nitrogen (N) contained in the SiO ₂ film (in atomic percent) are lower than those detectable by X-ray photoelectron spectroscopy. The results of the test indicate that the ALD SiO ₂ film is purely pure and has no measurable C and N contents. The SiO ₂ film formed by thermal oxidation of Si exhibits a similar purity as SiO ₂ deposited by ALD.

The book-like aspect of the present disclosure generally continuous, SiO ₂ layer of conformal method, comprising continuously exposed on the surface of the substrate deposited on the substrate to a first precursor Si to produce Si precursor bonded to a first surface of the substrate a single layer of molecules. The first Si precursor molecules bonded to the surface of the substrate are exposed to a first source of oxygen wherein oxygen from the source of oxygen reacts with the first Si precursor molecules bonded to the surface of the substrate. The substrate surface can be repeatedly exposed to the first Si precursor molecules and the first oxygen source until a continuous, conformal SiO ₂ layer having a predetermined thickness is produced on the surface of the substrate.

Flowchart of an example process of FIG 2 depicts an embodiment, the process by ALD deposition system for continuous and conformal SiO _2.

At 210, the substrate can be placed in a reaction chamber suitable for use in an ALD deposition process. The chamber may include an internal volume, a susceptor, and a gas distribution assembly, the internal volume may be sealed and evacuated by a vacuum pump, the pedestal is used to hold one or more wafers, and the gas distribution assembly is used to transport the Si precursor of the gas. The source and oxygen are sourced to the reaction chamber and/or wafer surface. In various embodiments, the substrate can be a germanium wafer.

At 220, the substrate may be heated to a predetermined temperature in a predetermined temperature silicon precursor on the substrate surface will be absorbed in and reacted with a source of oxygen, to deposit a monolayer on the substrate surface or sub-SiO ₂ single layer. In various embodiments, the substrate can be heated by any suitable heating source, including but not limited to a heat lamp and/or by conductive heating from a susceptor that holds the substrate. Heating can be monitored by suitably positioned thermocouples and/or pyrometers that can be placed externally, within the chamber, and/or operatively associated with the chamber assembly.

At 230, a Si precursor can be introduced into the reaction chamber such that the surface of the substrate can be exposed to the Si precursor of the gas. The Si precursor of the gas can contact the surface of the substrate and a portion is absorbed onto the surface.

In one or more embodiments, the Si precursor can be liquid at room temperature and pressure in a standard environment. In various embodiments, the liquid Si precursor can be contained in a container (for example, an ampoule) such that the Si precursor can be heated to increase the volatility and vapor pressure of the Si precursor and produce a reaction that can be introduced into the reaction. The Si precursor of the gas in the chamber. The carrier gas can be passed through the ampoule to carry the precursor to the processing chamber.

In some embodiments, the Si precursor is solid at room temperature and pressure in a standard environment. The solid precursor can be contained in a container (for example, an ampoule) that can be heated to sublimate the precursor. The carrier gas can be passed through the ampoule to carry the precursor to the processing chamber.

In some embodiments, the flow of the Si precursor of the gas can be directed toward the surface of the substrate, for example by an ALD injector or showerhead, without the need to fill the reaction chamber with the Si precursor. In various embodiments, the Si precursor of the gas flows into the processing region, and the processing region can be separated from the adjacent processing region by the air curtain in the same processing chamber.

In one or more embodiments, the hafnium precursor comprises a compound of R ₃ Si:NY ₃ wherein R is hydrogen, a halogen selected from the group consisting of Cl, Br, and I, a linear or branched C _{a 1-} C ₁₀ alkyl group, a linear or branched C ₁ -C ₁₀ alkoxy group and/or a C ₆ -C ₁₀ aryl group, and a Y-based hydrogen group selected from the group consisting of Cl, Br and I Halogen, linear or branched C ₁ -C ₁₀ alkyl, linear or branched C ₁ -C ₁₀ alkylfluorenyl and/or C ₆ -C ₁₀ aryl.

In one or more embodiments, the Si precursor can be reacted with oxygen plasma and/or a gas including ozone.

At 240, the Si precursor can be absorbed onto the surface of the substrate. In some embodiments, the absorption process can be a physical absorption interaction. In one or more embodiments, the absorption process can be a chemical absorption interaction. In various embodiments, the Si precursor can interact with the substrate surface at one or more bonding sites and/or by, for example, dipole-dipole interaction. In various embodiments, the absorption can be by chemical absorption where the Si precursor is bonded to the surface of the substrate.

In one or more embodiments, the absorber is self-limiting such that a single or sub-monolayer of Si precursor is formed on the surface of the substrate. In various embodiments, the Si precursor additionally exposed to the gas does not produce a thicker layer of absorbed Si precursor over a predetermined reaction temperature range.

At 250, an oxygen source can be introduced into the reaction chamber such that the substrate surface and/or the membrane that has absorbed the Si precursor can be exposed to the oxygen source. In various embodiments, the source of oxygen can be directed, for example, by an ALD injector toward the surface of the substrate without enriching the reaction chamber with an oxygen source. in In various embodiments, the source of oxygen may be evacuated through the vacuum conduit(s) prior to filling the reaction chamber and/or exposing portions of the substrate that are not under the syringe delivery conduit.

In one or more embodiments, the Si precursor can be reacted with oxygen plasma and/or a gas including ozone at a temperature in the range of about 400 ° C to about 700 ° C to form a deposited, continuous, and conformal The SiO ₂ layer is on the substrate.

At 260, the Si precursor can be reacted with an oxygen source to deposit continuous and conformal SiO ₂ on the surface of the substrate. The deposited metal layer can be a single layer or a sub-monolayer thickness, and no detectable carbon or nitrogen is included in the SiO ₂ layer. The reaction of the Si precursor with the oxygen source to deposit a layer of SiO ₂ on the surface of the substrate completes the cycle of ALD exposure and reaction.

In various embodiments, the amine compound and/or one or more organic compounds can be released from the surface of the substrate and/or the deposited SiO ₂ layer at the reaction temperature of the substrate. The released compound can be evacuated from the reaction chamber by vacuum.

In various embodiments, the SiO ₂ layer formed on the surface of the substrate can be conformal to various surface features, including sidewalls and bottom walls of one or more trenches formed in the surface of the substrate such that a substantially uniform SiO ₂ single The layer or sub-monolayer is deposited on all exposed surfaces at each cycle. Some features protrude from the surface of the substrate such that the features have top and sides.

In one or more embodiments, the substrate surface can include from about 10:1 to about 100:1, from about 20:1 to about 100:1, from about 10:1 to about 50:1, from about 20:1 to One or more special aspect ratios in the range of about 50:1 And the ruthenium precursor forms a conformal layer on one or more features. In various embodiments, the substrate surface can be a portion of an electronic component.

In one or more embodiments, the surface features can have a size in the range of from about 100 nm to about 3.5 [mu]m, from 100 nm to about 700 nm, from 1 [mu]m to about 3.5 [mu]m. In various embodiments, the trench depth can be from about 2 [mu]m to about 3.5 [mu]m and the aspect ratio can be 50:1.

In one or more embodiments, the trench width can be from about 10 nm to about 30 nm and the trench depth can be from 100 nm to about 1000 nm. In various embodiments, the trench depth can be from about 50 nm to about 100 nm, and the trench depth can be from 1 μm to about 3.5 μm. In one or more embodiments, the one or more component features can be trenches having a trench depth in the range of from about 1 um to about 3.5 um. In one or more embodiments, the one or more component features can be trenches having a trench depth in the range of about 100 nm to about 700 nm.

At 270, a cycle of introducing a Si precursor to expose the surface of the substrate and introducing an oxygen source at the reaction temperature to form an additional SiO ₂ layer on the surface of the substrate may be repeated one or more times to form a deposited SiO ₂ layer having a predetermined thickness. . In various embodiments, the exposure and deposition cycles can be repeated a sufficient number of times to form a SiO ₂ layer having a thickness in the range of from about 5 Å to about 300 Å. In various embodiments, SiO ₂ can be deposited at a rate of from about 0.8 to about 1.5 Å/sec.

At 280, a post deposition process of the metal layer and/or substrate can be performed. In one or more embodiments, the post deposition process can include one or more of UV curing, thermal annealing, post vapor annealing, and/or plasma processing. In various embodiments, UV curing can be performed using a broadband (200 nm-4000 nm) light source for a time in the range of from about 1 minute (min) to about 6 min, wherein the UV cure densifies the deposited SiO ₂ film layer, and relative to For thermally grown yttrium oxide, the wet etch rate ratio (WERR) in 1% HF is reduced from about 12.0 to about 6.4, as shown in Table 2. In various embodiments, UV curing can be carried out in a temperature range of from about 350 °C to about 450 °C, or at about 400 °C.

In various embodiments, thermal annealing (rapid heat treatment - TRP) can be carried out at a temperature above the temperature of the substrate in the range of from about 30 seconds (sec) to about 150 sec, or about 120 sec. In various embodiments, the RTP can be implemented at about 1050 °C. In various embodiments, RTP can be implemented in the atmosphere of N ₂ and/or O ₂ , where RTP improves film quality and reduces the ratio of wet etch rates (for example, from 9.9 to 5.1 for N ₂ RTP, Or 5% to 6.5 for O ₂ RTP.

In various embodiments, the post-vapor annealing may be carried out at a water concentration of from about 10% to about 50% at a temperature of about 550 ° C for about 30 minutes. Post-vapor annealing improves film quality and reduces the rate of wet etch rate (for example) from 8.8 to 6.5 for a temperature of about 550 ° C for a treatment of about 30 min.

Figure 3 depicts a conformal SiO ₂ layer 125 deposited between the Si precursor and the source of oxygen above the surface features 118 by an ALD reaction, the surface features 118 being trenches, perforations or fabricated electronic structures (For example, FINFET).

Figure 4 shows a portion of a processing chamber that includes a plurality of gas injectors for simultaneously processing a plurality of wafers such that the wafers undergo the same process flow. For example, as shown in FIG. 4, the processing chamber 100 has four gas injector assemblies 30 and four wafers 60. At the beginning of the process, the wafer 60 can be located between the injection assemblies 30. Rotating the Trojan-style pedestal 66 at 45° will cause each wafer 60 to be moved to the syringe assembly 30 for film deposition. This is the position shown in Figure 4. An additional 45° rotation will move the wafer 60 away from the syringe assembly 30. Using an ALD injector, the film is deposited on the wafer during movement of the wafer relative to the syringe assembly. In some embodiments, the pedestal 66 is rotated such that the wafer 60 does not stop below the syringe assembly 30. The number of wafers 60 and gas distribution components 30 can be the same or different.

In one or more embodiments, system 100 further includes a pump system coupled to the processing chamber. The pump system is generally configured to evacuate the gas flow of the processing chamber by one or more vacuum ports. A vacuum system is disposed between each gas crucible to evacuate the gas flow of the processing chamber after the gas stream reacts with the surface of the substrate and further restricts cross-contamination between the precursors.

This type of atomic layer deposition system (i.e., in which a plurality of gas systems respectively flow simultaneously toward the substrate) is referred to as space ALD. In operation, the substrate 60 is transferred (e.g., by a robotic arm) to the processing chamber and can be placed on the susceptor before or after entering the processing chamber. The susceptor moves through the processing chamber through the gas distribution assembly 30 below (or above). In the embodiment shown in Figure 4, the base passes through a rotary Trojan processing system in a circular path.

A processing chamber having a plurality of gas injectors can be used to simultaneously process a plurality of wafers such that the wafers undergo the same process flow. For example, as shown in FIG. 4, the processing chamber 100 has four gas injector assemblies 30 and four wafers 60. At the beginning of the process, wafer 60 can be placed between syringe assemblies 30. Rotating the Trojan-style pedestal 66 at 45° will cause each wafer 60 to be moved to the syringe assembly 30 for film deposition. This is the position shown in Figure 4. An additional 45° rotation will move the wafer 60 away from the syringe assembly 30. Using an ALD injector, the film is deposited on the wafer during movement of the wafer relative to the syringe assembly. In some embodiments, the pedestal 66 is rotated such that the wafer 60 does not stop below the syringe assembly 30. The number of wafers 60 and gas distribution components 30 can be the same or different. In some embodiments, the number of wafers being processed is the same as the number of gas distribution components. In one or more embodiments, the number of wafers processed is an integer multiple of the number of gas distribution components. For example, if there are four gas distribution components, there are 4x processed wafers, where x is an integer value greater than or equal to one.

The processing chamber 100 shown in FIG. 4 is only representative of one possible configuration and should not be construed as limiting the scope of the disclosure. Here, the processing chamber 100 includes a plurality of gas distribution assemblies 30. In the illustrated embodiment, there are four gas distribution assemblies 30 that are evenly spaced about the processing chamber 100. The processing chamber 100 is shown as an octagon, however, cooked It will be understood by those skilled in the art that this is a possible shape and should not be construed as limiting the scope of the disclosure.

The processing chamber 100 includes a substrate support device, shown as a circular base 66 or a base assembly. A substrate support device, or susceptor 66, can move a plurality of substrates 60 under each gas distribution assembly 30. The load lock 82 can be coupled to one side of the processing chamber 100 to allow the substrate 60 to be loaded into/unloaded from the chamber 100.

Processing chamber 100 can include a plurality (or a set) of first processing stations 80 disposed between any or each of a plurality of gas distribution assemblies 30. In some embodiments, each of the first processing stations 80 provides the same processing to the substrate 60.

The number of processing stations and the number of different types of processing stations may vary depending on the process. For example, one, two, three, four, five, six, seven, or more processing stations may be disposed between the gas distribution assemblies 30. Each processing station can independently provide different processing than each of the other group processing stations, or can have a mix of the same kind and different kinds of processing. In some embodiments, one or more individual processing stations provide different processing than one or more other individual processing stations.

The extent to which the substrate surface 115 is exposed to each gas can be determined, for example, by the rate of flow of each gas from the gas crucible and the rate of movement of the substrate 60. In an embodiment, the flow rate of each gas is controlled so as not to remove the absorbed precursor from the substrate surface 61. The width between each of the separators, the number of gas imperfections disposed on the processing chamber 100, and the number of passes of the substrate across the gas distribution assembly may also determine the surface of the substrate. 61 is exposed to various gases. Therefore, the amount and quality of the deposited film can be optimized by changing the factors referred to above.

Although the process has been described in conjunction with a gas distribution assembly that directs the gas flow downwardly toward the substrate disposed below the gas distribution assembly, it will be appreciated that this orientation can be different. In some embodiments, the gas distribution assembly directs the gas flow upward toward the surface of the substrate. When used in the context of this specification and the accompanying claims, the word "passing through" means that the substrate has been moved from one side of the gas distribution component to the other such that the entire surface of the substrate is exposed. Each gas stream from the gas distribution plate. The word "passing through" does not imply any particular orientation of the gas distribution component, gas flow or substrate position, unless otherwise stated.

In some embodiments, the susceptor for carrying the substrate is a carrier that helps to form a uniform temperature throughout the substrate and is rotatable such that the substrate moves in a circular path. The pedestal has a top surface for carrying the substrate. The pedestal can be a heated pedestal such that the substrate can be heated for processing. As an example, the pedestal 66 can be heated by a radiant heat lamp, heating plate, resistive coil, or other heating device disposed beneath the susceptor.

In yet another embodiment, the top surface of the pedestal includes a recess to receive the substrate. The pedestal is generally thicker than the thickness of the substrate such that a pedestal material is present beneath the substrate. In some embodiments, the recess is sized such that when the substrate is disposed inside the recess, the first surface of the substrate remains horizontal to the top surface of the pedestal or substantially coplanar with the top surface of the pedestal. In other words, the recesses of some embodiments are sized such that when the substrate 60 is disposed in the recess, the first surface of the substrate 60 does not protrude from the base Above the top surface of the seat. As used in this specification and the accompanying claims, the term "substantially coplanar" means that the top surface of the wafer is coplanar with the top surface of the susceptor assembly within ±0.2 mm. In some embodiments, the top surface is coplanar within ±0.15 mm, ±0.10 mm, or ±0.05 mm.

The rotation of the carousel can be continuous or discontinuous. During the rotation process, the wafer system is continuously rotated so that the wafers are sequentially exposed to each of the injectors. In a discontinuous process, the wafer can be moved to the syringe region and stopped, and then moved to the region 84 between the injectors and stopped. For example, the carousel can be rotated such that the wafer moves from the area in the middle of the syringe across the syringe (or stops adjacent to the syringe) to the area intermediate the next syringe that he can pause again. The pause between the injectors can provide time (e.g., exposure to plasma) for additional processing steps between each layer of deposition.

In some embodiments, the processing chamber includes a plurality of air curtains 40. Each gas curtain 40 can form a barrier to avoid or minimize the transfer of process gas from the gas distribution assembly 30 from the gas distribution assembly region and to avoid or minimize the transfer of gas from the processing station 80 from the processing station region. The gas curtain 40 can comprise any suitable combination of gas and vacuum flow that isolates individual processing regions from adjacent regions. In some embodiments, the air curtain 40 is a clean (or inert) gas stream. In one or more embodiments, the air curtain 40 is a vacuum flow that removes gas from the processing chamber. In some embodiments, the air curtain 40 is a combination of a cleaning gas stream and a vacuum stream such that there is a (sequential) cleaning gas stream, a vacuum gas stream, and a cleaning gas stream. In one or more embodiments, the air curtain 40 is a combination of a vacuum flow and a flow of cleaning gas such that there is a (sequential) vacuum flow, a cleaning gas flow, and a vacuum flow. The air curtain 40, shown in Figure 4, is located between each gas distribution assembly 30 and the processing station 80, but it will be understood that the air curtain can be located at any point or points along the processing path.

In the embodiment shown in FIG. 5, a set of second processing stations 85 are disposed between the first processing station 80 and the gas distribution assembly 30 such that the substrate 60 that is rotated by the processing chamber 100 will be encountered. Before any of the second set of gas distribution components 30, first processing station 80, and second processing station 85, encounter (depending on where the substrate 60 begins) gas distribution assembly 30, first processing station 80, and Two processing stations 85. For example, as shown in FIG. 5, if the substrate begins at the first processing station 80, the first processing station 80 will be encountered (sequentially) before encountering the second group of first processing stations 85, Gas distribution assembly 30 and second processing station 85. In various embodiments, processing station 85 can be adapted to perform the post deposition process described above.

The processing station can provide any suitable type of processing to the substrate, film or substrate assembly on the substrate. For example, UV lamps, flash lamps, plasma sources, and heaters. The wafer system then moves between the location with the gas distribution assembly 30 to a location having, for example, a showerhead that delivers plasma to the wafer. The plasma station is referred to as a processing station 80. In one or more examples, a tantalum nitride film can be formed by plasma treatment after each deposited layer. As long as the surface is saturated, since the ALD reaction is (theoretically) self-limiting, additional exposure to the deposition gas will not cause damage to the film.

Figure 6 depicts an example embodiment of a circular gas distribution assembly.

When the substrate moves around the processing chamber, the top surface of the substrate facing the crucible is repeatedly exposed to the reaction gas A (Si precursor) from the gas crucible 425 and the reaction gas B (oxygen source) from the gas crucible 435, and There is a cleaning gas from the gas crucible 445 between. The injection of cleaning gas is designed to reduce or prevent the arrival of precursors prior to exposing the surface of the substrate to the next precursor and to help remove unreacted material from the previous exposure of the precursor. After each exposure to various gas streams (eg, reactive gases or cleaning gases), the gas stream is evacuated by a pump system through vacuum crucible 455. Since the vacuum crucible can be placed on both sides of each gas crucible, the gas flow is evacuated through the vacuum crucible 455 on both sides. Therefore, the gas flow from the individual gas helium flows vertically downward toward the substrate surface 110 toward the first surface of the substrate 60 and eventually flows upward toward the vacuum crucible 455. In this way, each gas can be evenly distributed throughout the substrate surface 110. The substrate 60 can also be rotated when the substrate 60 is exposed to various gas streams. Rotation of the substrate may be useful in preventing the formation of strips in the formed layer. The rotation of the substrate can be continuous, or in a separate step, and can occur when the substrate passes under the gas distribution assembly 30, or when the substrate is in a region before and/or after the gas distribution assembly 30.

The susceptor assembly is located within the processing chamber and rotates the at least one substrate about the axis of rotation in a substantially circular path. As used in this specification and the accompanying claims, the term "substantially circular" means that the path is intended to be circular if the substrate is to be fully rotated. The base assembly has a top surface defined by an inner peripheral edge and an outer peripheral edge. Base assembly Located below the gas distribution assembly such that the top surface of the base assembly faces the front surface of the gas distribution assembly.

In some embodiments, one or more layers may be formed during a plasma enhanced atomic layer deposition (PEALD) process. In some processes, the use of plasma provides sufficient energy to promote species into an excited state where surface reactions become favorable and suitable. The introduction of the plasma into the process can be continuous or pulsed. In some embodiments, a continuous pulse of precursor (or reactive gas) and plasma is used to treat a layer. In some embodiments, the reactants are ionized locally (i.e., in the processing zone) or distally (i.e., outside the processing zone). In some embodiments, distal ionization can occur upstream of the deposition chamber such that ions or other energy or luminescent species do not directly contact the deposited film. In some PEALD processes, the plasma is generated from outside the processing chamber, such as by a remote plasma generator system. The plasma can be produced via any suitable plasma generation process or technique known to those skilled in the art. For example, the plasma can be generated by one or more of a microwave (MW) frequency generator or a radio frequency (RF) generator. The frequency of the plasma can be adjusted depending on the particular reaction species that will be used. Suitable frequencies include, but are not limited to, 2 MHz, 13.56 MHz, 40 MHz, 60 MHz, and 100 MHz. While plasma can be used during the deposition process disclosed herein, care should be taken that plasma may not be needed. Indeed, other embodiments are directed to the need for a plasma deposition process under very mild conditions.

In accordance with one or more embodiments, the substrate is processed prior to and/or after formation of the layer. This process can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is from The first chamber is moved to a separate, second chamber for further processing. The substrate can be moved directly from the first chamber to a separate processing chamber, or the substrate can be moved from the first chamber to one or more transfer chambers and then moved to a desired, separate processing chamber. Thus, the processing device can include a plurality of chambers in communication with the transfer station. This type of device can be referred to as a "cluster tool" or a "cluster system" and the like.

In general, a cluster tool is a modular system, and a modular system includes a plurality of chambers that perform various functions, including substrate center finding and orientation, degassing, annealing, deposition, and/or etching. In accordance with one or more embodiments, the cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber accommodates a robotic arm that can transport the substrate back and forth between the processing chamber and the load lock chamber. The transfer chamber is typically maintained in a vacuum and provides an intermediate station for transferring the substrate back and forth from one chamber to another and/or back and forth to a load lock chamber located at the forward end of the cluster tool. Two known clustering tools available for this disclosure are Centura® and Endura®, both available from Applied Materials, Inc. of Santa Clara, California. However, the proper configuration and combination of chambers can be varied for the purpose of performing the specific steps of the processes described herein. Other processing chambers that may be used include, but are not limited to, periodic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemistry Cleaning, heat treatment (such as RTP), plasma nitridation, degassing, orientation, hydroxylation, and other substrate processes. Large by implementing the process in the chamber on the cluster tool Surface contamination of the substrate of gaseous impurities can be avoided and does not require oxidation prior to deposition of the subsequent film.

In accordance with one or more embodiments, when the substrate is moved from one chamber to the next, the substrate is continuously in a vacuum or "load locked" state and is not exposed to ambient air. The transfer chamber is therefore under vacuum and "evacuated" under vacuum pressure. An inert gas may be present in the processing chamber or in the transfer chamber. In some embodiments, an inert gas system is used as a cleaning gas to remove some or all of the reactants after formation of a layer on the surface of the substrate. In accordance with one or more embodiments, a cleaning gas is injected at the exit of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and/or other processing chambers. Therefore, the flow of the inert gas forms a curtain at the outlet of the chamber.

The substrate can be heated or cooled during processing. Such heating or cooling can be accomplished by any suitable means including, but not limited to, varying the temperature of the substrate support (e.g., the susceptor) and flowing the heated or cooled gas to the substrate surface. In some embodiments, the substrate support comprises a heater/cooler, and the heater/cooler can be controlled to change the substrate temperature in a conductive manner. In one or more embodiments, the utilized gas (either the reactive gas or the inert gas) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater/cooler is located within a chamber adjacent the surface of the substrate to convect the substrate temperature.

The substrate can also be fixed or rotated during processing. The rotating substrate can be rotated continuously or in a prudent step. For example, the substrate can be rotated from start to finish throughout the process, or the substrate can be exposed to different A small amount of rotation between the reaction or cleaning gas. Rotating the substrate during processing (either continuously or in multiple steps) can help produce more uniform deposition or etching by minimizing, for example, the effects of local variations in gas flow geometry.

While the foregoing is a description of the embodiments of the present disclosure, other and further embodiments of the present disclosure may be made without departing from the basic scope of the disclosure, and the scope of the disclosure is determined by the scope of the following claims.

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Claims (20)

A method of depositing a film, comprising the steps of: placing a wafer having a surface in a reaction chamber; heating the wafer in a reaction chamber to a predetermined temperature; exposing at least a portion of the wafer to a stack The precursor is formed for a predetermined period of time to form a layer of tantalum on the wafer, the precursor comprising a compound having the general formula R ₃ Si:NY ₃ , wherein each R is independently selected from hydrogen, selected from One of the group consisting of Cl, Br and I is a halogen, a straight or branched C ₁ -C ₁₀ alkyl group, a straight or branched C ₁ -C ₁₀ alkoxy group and a C ₆ -C group _{a 10} aryl group, and each Y group is hydrogen alone, one selected from the group consisting of Cl, Br, and I, a halogen, a straight chain or a branched C ₁ -C ₁₀ alkyl group, a straight chain or a branch a C ₁ -C ₁₀ alkyl fluorenyl group and/or a C ₆ -C ₁₀ aryl group; exposing at least a portion of the wafer to an oxygen plasma and/or an oxygen source gas to be on the wafer The ruthenium layer reacts to form a ruthenium oxide film. The method of claim 1, wherein the predetermined temperature of the wafer is in the range of from about 50 °C to about 1000 °C. The method of claim 1, wherein the ruthenium precursor is a compound having the formula Me ₃ Si:L, wherein Me is a methyl group and L is a first or second amine, and the crystal The predetermined temperature of the circle is in the range of from about 400 °C to about 700 °C. The method of claim 3, wherein the ruthenium precursor is a compound having the formula X ₃ Si:L, wherein X is a group selected from the group consisting of Cl, Br, I, and Cl, Br, and I. The group of one halogen, L is a first amine or a second amine, and the predetermined temperature of the wafer is in the range of from about 400 °C to about 700 °C. The method of claim 4, the method further comprising the step of heating the ruthenium precursor to a temperature in the range of from about 20 ° C to about 200 ° C to treat the continuous stream of the ruthenium precursor as a vapor. Provided to the reaction chamber. The method of claim 1, wherein the reaction chamber comprises a plurality of processing regions, each of the plurality of processing regions being separated from the adjacent processing region by an air curtain, and the germanium precursor and the oxygen plasma and / or oxygen source gas is flowed into a plurality of separate processing zones. The method of claim 6 wherein each of the air curtains comprises a flow of cleaning gas having a source of vacuum on each side of the flow of cleaning gas. The method of claim 6, wherein the stream of the ruthenium precursor enters two or more processing regions, and the oxygen plasma and/or an oxygen source gas is provided for two or more different treatments. In the region, wherein the ruthenium precursor is flowed into a plurality of processing chambers that alternate spatially with the plurality of processing regions in which the oxygen plasma and/or the oxygen source gas flow. The method of claim 1, wherein the wafer surface comprises one or more component features of an aspect ratio in a range from about 10:1 to about 100:1, and the germanium precursor forms a conformal layer On the one or more component features. A method of depositing a SiO ₂ film on a wafer, comprising the steps of: exposing a wafer surface to a stack of precursors, wherein the germanium precursor comprises R ₃ Si:NY ₃ , wherein each R system is individually selected From hydrogen, one of the group selected from the group consisting of Cl, Br and I, a halogen, a straight or branched C ₁ -C ₁₀ alkyl group, a straight chain or a branched C ₁ -C ₁₀ alkoxy group And/or a C ₆ -C ₁₀ aryl group, and each Y group is independently selected from the group consisting of hydrogen, one selected from the group consisting of Cl, Br and I, a halogen, a straight chain or a branched C ₁ - a C ₁₀ alkyl group, a straight chain or a branched C ₁ -C ₁₀ alkyl fluorenyl group and/or a C ₆ -C ₁₀ aryl group, and wherein at least a portion of the ruthenium precursor is absorbed onto the surface of the wafer; heating The surface of the wafer is at a temperature ranging from about 450 ° C to about 650 ° C such that the absorbed tantalum precursor is decomposed on the surface of the wafer to form a single or sub-monolayer film; and exposing the surface The single or sub-monolayer ruthenium film and the surface of the wafer to a source of oxygen, wherein the source of oxygen reacts with the single or sub-monolayer ruthenium film to form a single or sub-monolayer SiO ₂ film. The method of claim 10, wherein the wafer is exposed The step of surface to a precursor includes passing the tantalum precursor through a showerhead and passing the wafer under the showerhead. The method of claim 11, wherein the wafer is a wafer and the germanium wafer is supported by rotating a pedestal such that the surface of the wafer passes under the showerhead Exposed to the ruthenium precursor for a predetermined amount of time. The method of claim 10, wherein the source of oxygen is an oxygen plasma and/or a gas comprising ozone. The method of claim 13, wherein the source of oxygen is the oxygen plasma combined with the gas comprising ozone. The method of claim 10, wherein the wafer surface comprises one or more component features of an aspect ratio in a range from about 10:1 to about 100:1, and the germanium precursor forms a conformal layer On the one or more component features. The method of claim 15 wherein the one or more component features have a plurality of trenches having a trench depth of between about 1 μm and about 3.5 μm. The method of claim 15 wherein the one or more component features have a plurality of trenches at a trench depth of between about 100 nm and about 700 nm. The method of claim 15 wherein the single or sub-monolayer SiO ₂ film conformally formed on the features of the elements comprises substantially no carbon or nitrogen contaminants. A method for forming a highly stable SiO ₂ film on a wafer by ALD, comprising the steps of: placing at least one germanium wafer into a susceptor in a reaction chamber; heating the at least one germanium wafer a temperature in the range of from about 450 ° C to about 650 ° C; a continuous flow of a precursor of a ruthenium introduced into the reaction chamber through a showerhead, wherein the ruthenium precursor comprises R ₃ Si:NY ₃ , wherein Each R is independently selected from the group consisting of hydrogen, one selected from the group consisting of Cl, Br, and I, a halogen, a straight or branched C ₁ -C ₁₀ alkyl group, a straight chain or a branched C. _{a 1} -C ₁₀ alkoxy group and/or a C ₆ -C ₁₀ aryl group, and each Y group is independently selected from the group consisting of hydrogen, one selected from the group consisting of Cl, Br and I, a straight chain Or a branched C ₁ -C ₁₀ alkyl group, a straight or branched C ₁ -C ₁₀ alkyl fluorenyl group and/or a C ₆ -C ₁₀ aryl group; providing an oxygen plasma and/or an oxygen source Gas in at least one processing region of the reaction chamber; rotating the susceptor such that the at least one ruthenium wafer passes under the showerhead, wherein at least a portion of the ruthenium precursor is absorbed into the twin On a surface of the circle, and the oxygen plasma and/or an oxygen source gas, wherein the oxygen plasma and/or an oxygen source gas react with the absorbed ruthenium precursor to form a SiO ₂ film. The method of claim 19, the method further comprising continuously treating the SiO ₂ film by a post deposition process, the post deposition process comprising a UV curing, a thermal annealing, a post-vapor annealing, and/or a plasma One or more of the treatments.