TW200826196A - Method to minimize wet etch undercuts and provide pore sealing of extreme low K (K < 2.5) dielectrics - Google Patents

Abstract

Methods of processing films on substrates are provided. In one aspect, the methods comprise treating a patterned low dielectric constant film after a photoresist is removed from the film by depositing a thin layer comprising silicon, carbon, and optionally oxygen and/or nitrogen on the film. The thin layer provides a carbon-rich, hydrophobic surface for the patterned low dielectric constant film. The thin layer also protects the low dielectric constant film from subsequent wet cleaning processes and penetration by precursors for layers that are subsequently deposited on the low dielectric constant film.

Description

200826196 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION Embodiments of the present invention mainly relate to the manufacture of an integrated circuit. More specifically, embodiments of the present invention relate to a process for depositing a thin layer comprising germanium, carbon, and optionally oxygen and/or nitrogen on a low dielectric constant layer. [Prior Art] Since the first invented integrated circuit components decades ago, the size of the integrated circuit geometry has been significantly reduced. Since then, integrated circuits have generally followed the two-year halving rule (often called the Moore rule), which means that the number of components on a wafer doubles every two years. Current manufacturing equipment routinely produces components with feature sizes of 〇·13μπι or even 0·1μηη, and future devices will soon be able to produce components with even smaller feature sizes. The ever-decreasing geometry of the components creates a need for an interlayer with a lower dielectric constant (k) value because the capacitive coupling between adjacent metal lines must be reduced to further reduce the size of the components on the integrated circuit. In particular, an insulator having a low dielectric constant is required, which has a dielectric constant of less than about 4.0. Recently, low dielectric constant organic germanium films having a dielectric constant of less than about 3.0 have been developed. An extremely low k (elt low k, ELK) organic germanium film having a dielectric constant of less than 2.5 has also been developed. A method for forming a low dielectric constant and very low dielectric constant organic germanium film has been used for a compound comprising an organic germanium compound and a hydrocarbon such as a hydrocarbon containing heat unstable 6 200826196 or a volatile group The gas mixture of the group is deposited to deposit the thin deposited film for post-treatment from the deposited thin unstable or volatile groups (e.g., organic groups). Removal of thermally unstable or volatile groups from the pores or pores in the film will reduce the dielectric constant of the film to about 1 for the dielectric constant air. The ashing process to remove the photoresist or bottom coating (BARC) can result in a lower k-value carbon and oxidation of the surface of the film. The surface of the subsequent wet etched low-k film will be removed and contribute to bottom seven and critical dimension (CD) losses. The porosity of the low &quot;electroconstant film can also result in the penetration of precursors deposited by subsequent layers of the application (e.g., BARC layers or intermetallic compounds, etc.). The diffusion of the barrier precursor precursor constant film causes leakage current in the device. Thus, there is still a need for a low dielectric process that can minimize damage during subsequent processing steps, such as deposition of wet layers such as BARC layers and subsequent layers of barrier layers. SUMMARY OF THE INVENTION The present invention generally provides a method of depositing a thin conformal sealing surface layer on a film on a substrate in a chamber. The patterned low dielectric constant film removes the photoresist, the film, and then removes the heat-deposited film in the film to cause nanometer scale, because the anti-reflective film is removed from the engraving process. Medium, undercut (undercut) on the film (TaN, the process of the porous low-k dielectric film, and the low dielectric constant method for the loss of the film include: from and then through the sink 7 200826196 A patterned conformal low dielectric constant film having any aspect ratio or via size is processed by a thin conformal layer having a controlled thickness between about 4 and about 100 A. The conformal layer comprises germanium and carbon on the surface of the patterned low dielectric constant film and optionally oxygen and/or nitrogen. In one embodiment, the deposition of the layer is included at a low RF power level In the presence of octamethylcyclotetraoxane, the ashing process of the photoresist is decarburized from the surface of the low dielectric constant film, and the surface thereof becomes &gt; hydrophilic. After ashing, The surface of the sealing layer is restored to a low dielectric constant The surface carbon concentration of the film provides a hydrophobic surface for the patterned low dielectric constant film. When the surface of the low dielectric constant film is hydrophobic, the wet etching rate of the low dielectric constant film is minimal. The low dielectric constant film can be protected and the undercut and CD loss can be prevented in a subsequent wet cleaning process that may be performed on the substrate. The thin layer provides a hydrophobic surface that prevents moisture from being absorbed into the low dielectric constant film. After the photoresist is ashed, the surface of the low dielectric constant film becomes oxidized and includes hydrogen hydroxide (OH). The surface absorbs moisture and greatly increases its I / dielectric constant. The thin layer deposition removes the moisture absorbed in the surface and removes the 0H radical on the surface of the low dielectric constant film, thereby restoring the low dielectric constant. The deposition of the thin layer provides protection against further A hydrophobic seal layer for moisture absorption. A thin conformal layer can be deposited on any coating or patterned film containing 0H, NH or NH2 groups on the surface (including oxides on the surface (eg Cu/CuO or A1/) Dielectric of A1203) Thin film and metal film) as a protective layer to prevent moisture adhesion and wet chemical etching, or as a hole 8 200826196 layer to prevent the penetration of precursors or chemicals. The thin layer can also be used as a sealing hole The layer is used for a porous dielectric film or a metal film having an OH, NH or NH2 group on the surface.

Embodiments of the present invention provide a method of depositing a thin conformal layer comprising tantalum, carbon, and optionally oxygen and/or nitrogen on a patterned substrate. In one aspect, embodiments of the present invention provide a method for protecting a patterned low dielectric constant film after the photoresist for patterning a low dielectric constant film is removed from the film. In other aspects, embodiments of the present invention provide a method of controlling the critical dimension of a metal line in an innterconnect, and a method of controlling the thickness of the deposited layer between about 4A and about 100 people. In one embodiment, a low dielectric constant film is patterned on the substrate using a photoresist and photolithography to form a vertical interconnect or a horizontal interconnect. The low dielectric constant film may be a film comprising stone, carbon, and optionally oxygen and/or gas. The low dielectric constant film may be deposited from a gas mixture comprising an organic cerium compound such as an organic decane or an organic decane. The gas mixture may also include an oxidizing gas. In one embodiment, the gas mixture comprises an organic ground compound and a pore former, such as a hydrocarbon, which is removed from the film after deposition of the film to create voids or voids in the film and to reduce the The dielectric constant of the film. The pore former may be removed by UV (ultraviolet) treatment, electron beam treatment, heat treatment, or a combination thereof. 9 200826196 A method of forming a porous low dielectric constant film is further described in detail in commonly assigned U.S. Patent No. 6,93,651, and U.S. Patent No. 7,060,036, incorporated herein by reference. It should be noted that low dielectric constant films having other compositions and/or deposited from different gas mixtures can be employed in embodiments of the present invention. It is also worth noting that other films than low dielectric constant films can be used in embodiments such as any film having a surface comprising 〇H, NH or NH2 groups. In summary, the applicable film has an oxygen-rich or nitrogen-rich surface. This surface selectively deposits a film comprising ruthenium, carbon and optionally oxygen and/or nitrogen thereon. As defined herein, the oxygen-rich surface has a Si: 矽 (矽: oxygen) ratio of between about 1:1 and about 1:3. As defined herein, the ratio of Sl:N (矽:nitrogen) of the nitrogen-rich surface is between about 1:1 and about 1:2. While the film can be deposited on an oxygen-rich or nitrogen-rich surface, the film generally does not grow on the carbon-rich surface, and thus, the deposition of the film on the oxygen-rich or nitrogen-rich surface can be described as a selective deposition process. Octamethylcyclotetrasiloxane (J 0MCTS) is an example of a precursor that can be applied to the deposition of the thin layers described herein. In addition to octamethylcyclotetraoxane, the formula is Rx- The precursor of Si-(〇R,)y is also used to form a conformal layer, such as dimethyldimethoxy oxime, in a suitable process window (pr〇cess wincj〇w). (CH3)2-Si-(〇_CH3)2, where each R = H, CH3, CH2CH3 or other radical 'each r, = CH3, CHzCH3 or other alkyl, X has a range of values 4, y ranges from 〇 to 4, while x + y = 4. Other precursors that can be used include organic diterpene 10 with a structure of (Rx-si-0-Si-Ry)z 200826196, for example 1 '3-Dimethyldioxane (cHs-SiHyO-SiHyCHs), 1,1,3,3 -, tetramethyldioxane ((CH3)2-SiH-0-SiH-(CH3) 2), hexamethyldi^ _ rustic burning ((CH3)3-Si-〇-Si-(CH3)3), etc. Other applicable precursors include production + long organic decane (Rx-Si-〇) y, where the value of y is greater than 2, the range of values of X g _ is 1 to 2, and rx = ch3, CH2CH3 or other Group may be applied @ ^, I comprises an organic silicon compound having cyclic quilt Axis cameras 3 or more silicon atoms, and the structure further comprises a% or more ring oxygen atom Ο

The cyclic organic oxime compound commercially available has a ring having alternating oxime and oxygen atoms' and one or two alkyl groups bonded to a ruthenium atom. For example, a bad organic compound can include one or more of the following compounds: hexamethylcyclotrioxane (-Si(CH3)2-0)3-ring, 1 '3' 5,7-tetradecyl环四石夕氧烧(TMCTS) (-SiH(CH3)2-0 such as ring, octadecylcyclotetraoxane (OMCTS) (-Si(CH3)2-0-) 4-ring, and 5,7,9-pentamethylcyclopentaoxane (-SiH(CH3)-0-) 5-ring. The thin layer comprises ruthenium, carbon, and optionally oxygen. In another embodiment The precursor may be a cerium-containing and nitrogen-containing precursor for depositing a thin conformal layer comprising cerium, nitrogen, and optionally carbon. The precursor may include a linear decazane and a cyclic decazane. The linear decazane may comprise an R-Si-NH-Si-R' structure wherein R = CH3, CH2CH3 or other alkyl group, R' = H, CH3, CH2CH3 or other alkyl group. The (Rx-Si-NH)Y structure may be included, wherein the value of y is greater than 2, the value of x ranges from 1 to 2, and RX = CH3, CH2CH3 or other alkyl groups. The cyclic decazane compound may include a ring structure of three or more germanium atoms, and the ring structure further includes one or more Nitrogen ion. Commercially available ring type 矽 11

200826196 Nitrogen compound includes a ring having alternating cleavage and ambience atoms, and one or a group bonded to a ruthenium atom. For example, a cyclic decazane compound can be used as a substance: 1,2,3,4,5,6,7,8-octamethylcyclotetrazet, 1,2,3,4,5,6- Hexamethylcyclotrifluoride, abbreviated; 1,3,3,5,5-hexamethylcyclotriazane, and 1,1,3,3,5,5,7,7-octamethyl The ring is broken with nitrogen. Fig. 1A shows an example of a low dielectric constant film on a substrate 100. FIG. 1B shows the photoresist 104 patterned in the low dielectric constant film 102. The photoresist is then removed from the low dielectric constant by, for example, photoresist removal or ashing. Fig. 1C shows the low dielectric constant 102 after the photoresist 106 is patterned into the interconnect 106 and the photoresist is removed. Thin conformal layer 108 (ie, having a thickness of from about 4 A to about 100 A. The layer comprises a stone, carbon, and optionally oxygen and/or nitrogen, followed by a patterned low dielectric constant film surface, as shown in FIG. In the presence of a nominal rate, the layer may be deposited by reacting a gas mixture (such as a gas mixture comprising helium, oxygen, and carbon). The stone j and carbon are provided by an organic stone compound, such as eight. Indolyl naphthenes. Organic ruthenium compounds are typically injected into the chamber with a carrier gas. The carrier gas is helium. However, other inert gases, such as nitrogen, may also be used. After deposition of the layer, the substrate will be applied. Wet cleaning, Example 1 00: 1 HF solution. Subsequently, as shown in Figure 1 E, layer 1 10, for example, two burns to include

The film on the upper surface of the film is formed by a layer of the film: RF work such as a &gt;, oxygen, tetrahydrogen. Preferably, an argon gas such as a PVD 12 200826196 barrier layer or an ALD barrier layer (e.g., an ALD tantalum nitride (TaN) layer) may be deposited on the layer. Alternatively, as shown in FIG. 1F, a layer, such as a barrier anti-reflective coating (BARC) layer 120, may be deposited on layer 108 and filled with interconnects 106. In the presence of RF power, in a chemical vapor deposition chamber or a plasma enhanced chemical vapor deposition chamber, deposition can be carried out by reacting a gas mixture containing an organic compound, including strontium, carbon, and A layer comprising oxygen and/or nitrogen is included. Examples of chambers that can be used to deposit this layer include: PRODUCER® chambers with two isolated processing areas and DxZ® chambers, both of which are available from Santa Clara, California's Applied Materials' Inc. (USA) Applied Materials, Inc. of Santa Clara, Calif., is commercially available. The process conditions provided herein are provided for a 300 mm PRODUCER 8 chamber with two isolated processing zones. Therefore, the flow rate of the parent substrate processing area and each substrate is half of the flow rate in the chamber. Typically, in the chamber, during the process of depositing the layer on the substrate (J, the temperature of the substrate is maintained between about 150 ° C and about 4 ° C. For a 300 mm substrate The power value of the supplied RF power is about i〇〇w or lower, for example between about 30 W and about 75 W. In general, the RF power can be provided at approximately 〇.l〇9 W/cm2 or lower, For example, between about 〇.〇33W/cm2 to about 0.082W/cm2. RF power can be supplied to a shower head, such as a gas distribution assembly, and/or a substrate holder for the chamber. The high frequency between 14MHz provides RF power 'better 13.56ΜΗζ. RF power can be periodic or pulse 13 200826196 rushed ° RF power can also be continuous or discontinuous. Head and substrate The spacing between the stents is greater than about 200 mils, such as between about 200 mils to about 1400 mils. The pressure in the chamber is about 1.5 Torr or higher, such as between about 1.5 T rr rr to about 8 Torr. The chamber can be injected at a flow rate between about SCCm and about 1 OOOsccm. The carrier gas will be approximately 10 A flow rate between Osccm and about 70 〇〇sccm Ο 注入 is injected into the chamber. In the chamber, the flow rate of the organic ruthenium compound (for example, octamethylcyclotetrazepine (〇MCTS, sccm)) and the carrier gas ( For example, the ratio of the flow rate of the injection chamber to the chamber is about 〇1 or higher. Depending on the aspect ratio of the patterned substrate, the layer can be deposited for a period of time, such as a time range of (M seconds to 600). Between f, to deposit a layer having a thickness between about Μ and about 100. Typically, when a higher aspect ratio is applied, the layer's product needs a longer time to provide a conformal surface. When the material acts as a precursor, a thin, uniform between 100A can be obtained in a single, as defined herein, ''self-precursor, such as no test. The thickness can be different through the pre-precursor. Different thicknesses. Under the thin condition, the presence of a thin layer is generally saturated, and the application of the above RF power flow rate ratio when applying a self-saturated organic germanium compound to reliably deposit a conformal thickness of only about 4A to about Layer. Apply the conditions provided here, thickness in 300mm substrate The layer of u. The saturated precursor is controlled by the choice of depositing a thin layer of precursor drive on the substrate for only one molecule layer over the length of deposition, due to the different sub-sizes that result in different precursors. The presence of a molecular layer, in the process for depositing the thin layer, hinders further deposition from the precursor to an additional layer. 14 200826196 The precursor may include a methyl group to inhibit the continued growth of the thin layer. 〇MCTS is a preferred self. Saturated Precursor 'This is because it contains a large number of methyl groups which cause a self-saturated deposition of one layer because the carbon in the thiol group provides sufficient inhibition of the surface of the carbon-rich film on which it is further deposited. That is, once the surface of the underlying substrate is covered by the OMCTS molecules, the conformal first layer can be deposited by the OCTS, and the presence of Si-CH3 bonds on the surface of the deposited layer provides a carbon-rich surface that inhibits further deposition until some The methyl group is removed by treatment of some other layer. Thus, the deposition of each molecular layer of the 0MCTS is well controlled, which will increase the step coverage of the final layer. In addition to the octadecylcyclotetraoxane, other useful precursors include diethoxymethyl decane (DEMS), hexamethyldioxane (HMDOS), and hexamethylene dioxane (HMDS). Other precursors containing Si, C and ruthenium may be used in the process, such as tridecyl decane, tetramethyl sulphate, and the like. X-ray photoelectron spectroscopy (XPS) analysis was performed on a low dielectric constant film that was not exposed to the ashing process and on a low dielectric constant film exposed to photoresist ashing. XPS analysis is also performed on a low dielectric constant film that is exposed to photoresist ashing and subsequent deposition of a thin layer thereon. [In accordance with an embodiment of the present invention, the thin layer is deposited by OCMC and contains germanium, carbon. And oxygen. XPS analysis showed that a thin layer was deposited on the ashed low dielectric constant film, which provided a higher carbon content on the surface of the film than the low dielectric constant film that was not processed by the deposited film ( The number of atoms. /. carbon). For example, an ashed low dielectric constant film may have about 3 atomic percent carbon, while a non-ashing low dielectric constant 15 200826196 thin film provides about 15 atomic percent carbon on the surface. Thus, in one aspect, the thin layer is a carbon rich layer. The thin layer has a carbon content of between about 5 atomic percent carbon and about 30 atomic percent carbon. The ashing step removes the carbon concentration of the surface of the low dielectric constant film, whereas depositing a thin layer on the ashed low dielectric constant film restores the surface carbon concentration. The XPS analysis also shows that the surface of the low dielectric constant film treated with the thin layer has a lower oxygen content than the surface of the low dielectric constant film which is not treated with the thin layer after ashing, because the ash film has been ashed. The OH group of the surface is replaced by a thin layer containing carbon. Replacing the OH groups of the surface of the ashed film with a thin layer containing carbon also reduces the dielectric constant of the ashed film. Figure 2 shows that the application of OMCTS to deposit a thin layer on a low dielectric constant film reduces the post-ashing dielectric constant of a film that has undergone one of three different ashing processes.

Wetting angle for low dielectric constant film before ashing and after ashing (ELK ILD (ie very low k interlayer dielectric) and ashed ELK ILD in Fig. 3), and after ashing And a low dielectric constant film having a thin OMCTS layer thereon was also measured. The result is shown in Fig. 3. In Figure 3, the deposition of a thin OMCTS layer on the ashed low dielectric constant film increases the wetting angle of the low dielectric constant film. The increased wetting angle shows that the thin OMCTS layer increases the hydrophobicity of the surface of the low dielectric constant film. Such an increase in hydrophobicity is desirable because the hydrophobic surface prevents moisture from adsorbing in the low dielectric constant film, where such adsorption will affect the film properties or at least cause the need to add some time for removing moisture. step. After wet cleaning after ashing, the effect of depositing a thin conformal OMCTS layer on the cross section of the interconnect was also examined. After the film is wet-cleaned in the process of 16200826196/parent/package in 100.1 HF&gt; trough, for areas with high trench density and low trench density in low dielectric constant films with or without thin omcts The trench profile is tested.

4A-4C illustrate a trench profile of a region with a high trench density. Figure 4A shows the trench profile before ashing and before wet cleaning. 4B and 4C are diagrams showing the trench profile on which the low dielectric constant film does not have and has a thin OMCTS layer, respectively, after ashing and after wet cleaning. Figure 4B shows that for trenches in low dielectric constant films that do not have a thin OMCTS layer, wet cleaning will cause a critical dimension loss of about 30 nm. Fig. 4C shows that such a CD loss would not be observed when a low dielectric constant film of a thin OMCTS layer was deposited thereon before wet cleaning. 5A-5C illustrate a trench profile of a region with a low trench density. Figure 5A shows the trench profile before ashing and before wet cleaning. The figures $b and $c show the low dielectric constant film on which the low dielectric constant film does not have a trench profile with a 'thin 0MCTS layer' after ashing and after wet cleaning. Figure 5b: For a trench in a low dielectric constant film having no thin 0MCTS layer thereon, the wet cleaning will cause a temple &amp; ^ J paper cut of greater than about 3 〇ηη. Fig. 5C shows that such an undercut will not be observed when a thin dielectric constant film of the genus &amp; i is deposited on the thin OMCTS layer before wet cleaning. Thus, the thin OMCTS layer provides a rich main surface anti-surface which in turn provides a hydrophobic surface for preventing the loss of critical dimensions and undercutting of the low-k film during the wet etching process. We can see that the thin layer provided in accordance with an embodiment of the present invention acts as a dense sealing layer and can be used to prevent the use of such a material (such as 17 200826196 as a BARC for depositing a BARC layer later, or as a A PVP barrier precursor or an ALD precursor (e.g., ald-precursor) of the deposition barrier layer penetrates into the porous low-k film deposited thereon by the thin layer. For example, after the photoresist ashing in the via etching and the vial first damasene process, the thin layer can be deposited on the low dielectric constant film. Subsequent BARC filling can be performed on the thin layer. The thin layer provides a plugging layer for the anti-soil BARC material to penetrate into the dielectric film. Then, a dielectric barrier between the low dielectric constant film and the underlying conductor material (such as copper) will be etched to expose the underlying conductive material after trench etching and photoresist removal. After etching the dielectric barrier, a reduction chemical reaction can be used to clean the conductive surface exposed by removing the dielectric barrier and to remove oxides (such as copper oxide (C u Ο) from the surface. )). The thin layer is then deposited on the sidewalls of the vias and trenches. The thin layer provides a layer of pores that prevents subsequent barrier layer precursors from penetrating into the low dielectric constant film. In an embodiment in which a BARC layer is deposited on a thin layer after wet cleaning of the substrate, the thin layer may be post-treated with a ruthenium (or other inert gas) plasma to adjust the carbon concentration of the surface of the thin layer and the thin The wetting angle of the layer. The wetting angle can be reduced to about 7 inches. 0 or less to promote wetting and deposition of the BARC layer. Figure 6 shows that the wetting angle is reduced as the plasma treatment time increases. Use mild process conditions (eg, RF power between about 3 〇w to about 10 ' w and He flow rate between about 1 〇〇 sccm and about 1 〇〇〇〇 sccm) for plasma processing The sealing properties of the thin layer will not be destroyed. If it is necessary to adjust the surface wetting or contact angle, the post-mortem plasma treatment can also be carried out before the deposition of the other layers (e.g., the A L D barrier layer) of the BARC layer on the thin layer. Different gases can be applied to the post-pulp treatment layer, such as 〇2, C〇2, N2〇, NH3, H2, nitrogen, nitrogen, nitrogen or combinations thereof. Plasma post treatment can alter the properties and properties of the surface of the layer, surface tension and surface contact angle. In another embodiment, a method of controlling the critical dimension of an interconnect centerline is provided. As described in the previous embodiments, this involves depositing a thin layer on the patterned low dielectric constant film. The patterned dielectric constant film may comprise an oxygen-rich or nitrogen-rich surface prior to being deposited on the patterned low dielectric constant film. After this layer, the flow of the precursor (e.g., 0 M C T S ) used to deposit the layer is terminated and removed from the chamber only by injecting a carrier gas (e.g., He carrier gas) into the chamber. The chamber can be purged or the chamber cleaned and pumped out. After purging and/or pumping the chamber, in one embodiment, an oxygen plasma treatment is performed in the chamber to treat deposition of the precursor onto the substrate (J and begin the next deposition cycle (eg, OMCTS deposition). In another mode, if a nitrogen-doped oxide or SiN layer is desired, the NH3 plasma treatment of H2 may or may not be added. The oxygen plasma may be from any oxygen-containing gas capable of producing oxygen radicals on the surface of the layer. Provided. For example, the body may include 〇2, C02, N20, or a combination thereof. The oxygen-containing gas may be injected into the chamber at a flow rate. The oxygen-containing gas will take a period of time to inject into the chamber for a period of from about 0.1 second to about 60. Between seconds, depending on the profile of the via pattern, the oxygen plasma will carry out the RF work between 50W and 1 000W to the thin deposition of thin layers such as metal deposition, or to be applied to the layer of the cavity. Adding oxidized gas to the chamber, the same/ditch ratio is supplied to the chamber at a frequency of 19 200826196 13.5 6 MHz. The mixing rate can be applied. In order to make the plasma treatment to the underlying layer (such as low-merase shock or damage is minimized) Good application low As between about 30 W and about 100 W, which corresponds to between about 0.082 W/cm 2. The electrical ground can be terminated by terminating the oxygen-containing gas flowing into the chamber, and then the thickness of the deposited layer can be measured. The flow causes it to flow into the chamber to deposit a thin layer of additional chambers and subsequently perform the above-described oxygen plasma treatment. Multiple cycles of the plasma treatment can be performed until the desired layer of the layer is obtained. The thickness of the layer in the wire can control the thickness of the metal wire as it is deposited. In another embodiment, a method of controlling the thickness of the sink between about 4 A and about 1 Torr is provided. The substrate is exposed in the presence of a plasma to deposit a layer on the substrate, and then uses a plasma generated from cerium-containing NH3, or an oxygen-containing gas selected from a group consisting of 02. The resulting electropolymerization, where the substrate is exposed to a ruthenium-containing precursor to deposit a layer, the step of treating the layer will be repeated until the layer is reached. • In yet another embodiment, a manufacturing package or Density of nitride A method of electrical barriers. In the case of a silent presence, exposure of an RF containing a gated pattern containing an oxygen-rich or nitrogen-rich surface to a germanium-containing precursor, a frequency-dependent RF work: a constant film) Power, for example, about 0.033 W/cm2 slurry treatment. Optional, recovering the amount of precursors. Purifying the deposition, purification and thickness of the chamber. After controlling, the upper layer of the substrate contains an oxygen-rich or cerium-rich precursor in the upper layer. Or without h2, co2, and N20. The above and the plasma are used to look at the thickness. Any oxide method includes, on an electrical substrate (which can be on the gate 20

200826196 deposits a layer and then treats the layer with a plasma produced from an oxygen-containing or nitrogen-containing gas (selected from the group consisting of 〇2, C〇2, n2〇, nitrogen-containing gas and nh3, containing h2) . The above-described ruthenium-containing precursor, the plasma at the method of controlling the critical dimension of the metal line in the interconnect, can also be used in a method of fabricating a dense dielectric spacer and a method of controlling the thickness of the layer from 4A to about 100A. While the foregoing is a description of the embodiments of the present invention, further or further embodiments may be devised without departing from the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The present invention, as outlined above, will be described in more detail with reference to the various embodiments of the present invention, in which FIG. It is to be understood that the drawings are only illustrative of the exemplary embodiments of the invention, and are not intended to 1A-1F are cross-sectional views showing a substrate structure at different stages of the process according to an embodiment of the present invention; FIG. 2 is a view showing an embodiment of the present invention, after ashing and low-leveling The dielectric constant (k) of the electro-continuous film, and the dielectric constant of the low-k dielectric film on which the thin OMCTS layer is deposited on the ashing (1 graph; FIG. 3 is a view showing an embodiment according to the present invention, The ashing contains or does not matter, in the 悖 悖 , , , , , , , 视 视 视 视 视 视 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 A graph of the wetting angle of a low dielectric constant film depositing a thin OMCTS layer; FIG. 4A is a schematic view of a trench profile (dense distribution) after ashing and before wet cleaning according to the prior art; FIG. 4B is a conventional view Schematic diagram of trench profile (dense distribution) after ashing and wet cleaning; Figure 4C is a schematic diagram of trench profile (dense distribution) after ashing and wet cleaning according to an embodiment of the present invention; Schematic diagram of a trench profile (iso structure/opening region) after ashing and wet cleaning according to prior art; Figure 5B is a trench profile (is 〇 structure/opening region after ashing and wet cleaning according to conventional techniques) Schematic diagram of FIG. 5C is a schematic rgj diagram of a trench profile (iso structure/opening region) after ashing and wet cleaning according to an embodiment of the present invention, and FIG. 6 is a diagram showing an implementation according to the present invention. A plot of the thin OMCTS layer wetting angle of the mode relative to the length of the plasma post-treatment of the layer. [Main component symbol description] 100 substrate 102 low dielectric constant film 104 photoresist 106 interconnect 108 thin conformal layer 110 layer 120 layer 22

Claims (1)

200826196 X. Patent Application Range: 1. A method of treating a film on a substrate in a chamber comprising: selectively depositing a thickness of 4 angstroms on an oxygen-rich or nitrogen-rich surface of the film The film is treated between 10 Å and containing ruthenium, carbon, and optionally a thin layer of oxygen or nitrogen, wherein the deposition of the layer includes the inclusion of S i, C, in the presence of RF power, and A precursor of sputum reacts. 2. The method of claim 1, wherein the precursor is selected from the group consisting of: a precursor of the formula Rx-Si-(OR')y, wherein R = H, CH3 , CH2CH3 or other alkyl, R' = CH3, CH2CH3 or other alkyl groups, x ranges from 0 to 4, y ranges from 0 to 4, and x + y = 4; with (Rx-Si -0-Si-Ry)z structure of an organic dioxane wherein RX = CH3, CH2CH3 or other alkyl group, Ry = H, CH3, CH2CH3 or other alkyl group; including (Rx-Si-0)y structure a cyclic organoaluminoxane, wherein RX = CH3, CH2CH3 or other alkyl; a cyclic organotelluric compound comprising a cyclic structure having 3 or more deuterium atoms, and the cyclic structure optionally comprising one or more oxygen Atom; and a cyclic organotelluric compound comprising alternating chopped and oxygen atomic rings and one or two alkyl groups bonded to the broken atoms. 3. The method of claim 1, wherein the precursor comprises a sulfhydryl group to inhibit continued growth of the thin layer. The method of claim 1, wherein the layer has a higher carbon content than the oxygen-rich or nitrogen-rich surface of the film, while the layer is on the film A carbon saturated surface layer is provided. 5. The method of claim 1, further comprising wet cleaning the substrate after the layer is deposited. 6. The method of claim 1, wherein the power value of the supplied RF power is about 0.109 W/cm12 or less. 7. The method of claim 1, wherein the pressure in the chamber is about 1.5 Torr or higher. 8. The method of claim 1, wherein a spacing of a showerhead in the chamber and a substrate support in the chamber is greater than about 200 mil 〇 9. as claimed in claim 1 The method further includes post treatment of the layer with a gas selected from the group consisting of ruthenium 2, C02, N20, NH3, H2, argon, argon, and nitrogen. The method of claim 1, further comprising 2 post-treating the layer, wherein the post-treatment of the plasma changes the surface characteristics of the layer of 200826196, and wherein the surface The characteristics are selected from the group consisting of surface tension and surface contact angle. 11. The method of claim 1, further comprising depositing a bottom anti-reflective coating on the layer. 1 2 The method of claim 1, further comprising depositing by atomic layer deposition or physical vapor deposition at a thickness of 4 to ιοοΑ and including Shixia and carbon, and optionally including oxygen and/or gas. A barrier layer is deposited on the layer. The method of claim 1, wherein the thin layer provides a dense layer that prevents the anti-reflective coating material and the ALD or PVD barrier layer precursor from penetrating into the film in. 1 4. A method of treating a substrate, wherein the substrate has a low-k dielectric film deposited on a surface thereof, the method comprising: selectively reacting a precursor by reacting in the presence of RF power A carbon-rich layer is deposited on an oxygen-rich or nitrogen-rich surface of the film, wherein the precursor comprises an element selected from the group consisting of ruthenium, carbon, oxygen, and nitrogen. The method of claim 14, wherein the carbon-rich layer has a thickness of between 4 angstroms and 100 angstroms. The method of claim 14, wherein the precursor is self-saturating. The method of claim 14, wherein the precursor is selected from the group consisting of: a precursor of the formula Rx-Si-(OR')y, wherein R = H, CH3, CH2CH3 or other alkyl, R, =CH3, CH2CH3 or other alkyl groups, X ranges from 0 to 4, y ranges from 0 to 4, and x + y = 4; An organic dioxane of the Rx-Si-0-Si-Ry)z structure, wherein RX = CH3, CH2CH3 or other alkyl group, Ry = H, CH3, CH2CH3 or other alkyl group; includes (Rx-Si-0) a cyclic organic oxane of the y structure, wherein RX = CH3, CH2CH3 or other alkyl; a cyclic organofluorene compound comprising a cyclic structure having 3 or more ruthenium atoms, and the cyclic structure optionally includes one or More oxygen atoms; and a cyclic organic ruthenium compound comprising a ring having alternating ruthenium and oxygen atoms, and one or two alkyl groups bonded to a ruthenium atom. 1 8. The method of claim 14, further comprising post-treating the carbon-rich layer with a gas selected from the group consisting of 〇2, C〇2, N2O, NH3, H2, , a group of nitrogen and nitrogen. 19. A method of processing a film on a substrate in a chamber, comprising: 26, 26,196, 196, and a thickness of between 4 and 100 Å by reacting a precursor in the presence of RF power. A carbon-rich layer is deposited on an oxygen-rich or nitrogen-rich surface of the substrate, wherein the precursor comprises an element selected from the group consisting of ruthenium, carbon, oxygen, and nitrogen. 20. The method of claim 19, further comprising exposing the carbon-rich layer to a plasma selected from the group consisting of ruthenium 2, C02, N20, NH3, H2, ruthenium, argon. And a compound of the group consisting of nitrogen is formed. 27