TWI277139B - Improved process for deposition of semiconductor filme - Google Patents

Abstract

Chemical vapor deposition processes utilize chemical precursors that allow for the deposition of thin films to be conducted at or near the mass transport limited regime. The processes have high deposition rates yet produce more uniform films, both compositionally and in thickness, than films prepared using conventional chemical precursors. In preferred embodiments, trisilane is employed to deposit thin films containing silicon are useful in the semiconductor industry in various applications such as transistor gate electrodes.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of fabricating a semiconductor circuit, such as a thin film containing germanium, germanium or carbon, and in particular to an improved semiconductor thin film. The deposition process 'produces a material having a large thickness and compositional uniformity in a chemical vapor deposition system. BACKGROUND OF THE INVENTION As the dimensions of microelectroic devices become smaller and smaller, the importance of the physical and chemical properties of the materials used in their manufacture becomes more and more important. Particularly suitable are those materials that use existing manufacturing tools to incorporate elements of the current generation. For example, mixed epitaxial germanium (SinGeJ and tantalum carbon compound (Su+yGe/y) alloys are suitable for use in bipolar and bipolar complementary metal oxide semiconductor (BiCMOS) devices. These advanced alloy materials serve as a base for a heterojunction bipolar transistor (HBT), a resistor for a bipolar complementary metal oxide semiconductor (BiCMOS) device, and as a complementary gold. A gate electrode of an oxygen semiconductor (CMOS) device or a device for use in various other integrated circuit components is known to be useful for single crystal, amorphous or polycrystalline silicon. The process of sand germanium (SiGe) and sand germanium carbon (SiGeC) alloys is typically a low pressure (LP) or ultra-high vacuum (UHV) batch thermal process or 127713⁄4 46pifl.doc/012 疋: Single wafer process. Single-wafer process is becoming more important' but there are still some problems. For example, in-wafer and wafer-to-wafer (wafer-to -wafer) Uniformity, deposition rate, and process reproducibility (repeataMlhy) remain the focus of traditional single-wafer processes, especially in Situ-doped semiconductor films. As wafers continue to increase in size Time (now 300mm wafers have been integrated into the manufacturing process), continuous uniformity to become more challenging. 专利 Patent Application Publication No. S60-43485 has disclosed the use of trioxane to make amorphous germanium at 300 ° C The film is used for a photovoltaic application, and Japanese Patent Application Laid-Open No. H5-6291 1 discloses that a film is produced using trioxane and decane at a temperature of 500 ° C or lower. No. H3-91239, H3-185817, H3-187215 and H02-155225 both disclose the use of dioxane, or some mention of trioxane. Technical aspects have been noted using dioxane and trioxane at relatively low deposition temperatures. Amorphous hydrogenated ruthenium. However, it is preferred to deposit semiconductor materials such as deposited tantalum, low hydrogen content amorphous tantalum and tantalum on the surface at a higher deposition rate without sacrificing good uniformity. It is still necessary. SUMMARY OF THE INVENTION The present invention has disclosed an improved deposition process for semiconductor thin films to produce germanium-containing and germanium-containing films. This method teaches the use of higher-order silanes and/or higher-grade brothels in chemical vapor deposition processes, and has provided improved processes for ruthenium-containing films, particularly for the semiconductor industry. SiGe), tantalum carbon (SiGeC) alloy film. These chemical precursors have reduced the thermal stability of pifl.doc/012 (carbon_source molecule) in sandstones, brothels, and conventional carbon source molecules. Accordingly, it is an object of the present invention to provide an improved deposition process for a semiconductor thin film using a special precursor such that the deposition process is directed closer to the same temperature as the conventional precursor or to a mass transfer limited growth. Within the scope of the mass transport limited growth regime. Temperatures that are subordinate to the non-uniformity of the concentration gradient and the varying film deposition rate, as well as subsequent thickness inconsistencies, can be avoided within this specification. Preferred chemical precursors include trioxane and trioxane in combination with dioxane. At a lower temperature than that used in conventional chemical precursors, uniform deposition can be achieved at higher film deposition rates. Another object of the present invention is to provide an improved deposition process for a semiconductor film that adjusts the flow rate versus temperature of a preferred precursor to achieve the same higher deposition rate than conventional precursors (e.g., decane) deposition. Or better uniformity. It is known that trioxane is superior to decane, and in particular, it can be applied to the deposition of a ruthenium-containing layer such as an active layer in an integrated crystal. It is yet another object of the present invention to provide an improved deposition process for a semiconductor thin film that teaches a method for progressively or continually changing process parameters such as temperature, temperature profile, pressure, reactant flow rate, and reactant partial pressure. In order to reduce or eliminate the objection concentration gradient, thickness inconsistency and varying film deposition rate. These methods can be used in conjunction with the use of higher decane and/or decane. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims. The following is a schematic diagram of a manufacturing process for forming a gate stack according to the preferred embodiment of the present invention; and FIG. 2 is a schematic diagram of a gate stack according to a preferred embodiment of the present invention. FIG. 3 is a schematic diagram of a manufacturing process for changing a set pomt during deposition according to a preferred embodiment of the present invention; FIG. 4 is a preferred enamel film. The relationship between the film thickness and the measurement site; Figure 5 shows a scanning electron photomicrograph of a film deposited with decane and decane; Figure 6 shows Scanning electron micrograph of the ruthenium film section of Figure 5; Figure 7 is a scanning electron micrograph of a ruthenium film deposited with trioxane and decane; Figure 8 shows Scanning electron microscopic phase of the 矽锗 film profile of Figure 7 Figure 9 shows a transmission electron photomicrograph of a preferred tantalum nitride film profile; Figure 10 shows Arrhenius obtained from decane, dioxane and trioxane under the following conditions. Fig. 11 is a graph showing the deposition rate of the ruthenium on the ruthenium oxide substrate at 600 ° C and 40 Torr, and the relationship between the rate of the SilicaTM MjfE, 8 12771涊6 pifl.doc/012, Fig. 12 The relationship between film thickness and position (posmon) at various times using silane (SilcoreTM) at 650 ° C, 40 ;; Figure 13 shows the deposition rate and diborane using trisane deposition Diagram of flow (diboraneflow); and Figure 14 shows the Rutherford Backscattering Spectrometry (RBS) elasticity of amorphous austenite deposited with trioxane at 600 ° C, 40 °* Elastic Recoil Detection (ERD) spectrum; Figure 15 shows a series of depositions with trioxane at 60 (TC, 650 ° C, 700 ° C and 750 (from bottom to top, respectively) X-ray diffraction patter n); Figure 16 is a transmission electron micrograph of a polycrystalline tantalum film section; Figure 17 is a selected area diffraction (SAD) diagram of a polycrystalline tantalum film section; Figure 18 is a scanning electron micrograph of a conformal amorphous ruthenium film; Figure 19 is a Latifah backscattering spectrum of a tantalum nitride film; and Figure 20 is a The elastic backlash detection spectrum of the Latifah backscattered spectrum of the tantalum nitride film. Brief description of the mark: 100: forming the gate dielectric layer 110: the surface of the dielectric layer of the stencil gate 12771l ifl.doc/012 120: depositing the germanium-containing film 130: depositing the metal layer 140: patterning the gate electrode 150: continuing the integrated circuit Fabrication 200: gate stack 210: gate dielectric layer 220: semiconductor substrate 230: germanium containing film 240: metal layer 300: preparation substrate 310: adjustment set point to 600 ° C 320: with 98% dioxane and 2 ° /〇Dioxane deposit 矽锗330: Deposition with 85% trioxane and 15% dioxane 矽锗340,360: Lower 3 °C set point 350: Deposition with 75% trioxane and 25% dioxane 370: Deposition of 矽锗380 with 65% trioxane and 35% dioxane: boron doping with 85% trioxane, 12% dioxane, 2°/〇 diborane and 1°/〇 dimethane Carbon-doped 矽锗390: 淸洁反应400: deposited with 90% trioxane and 10% dioxane

410: increasing the set point to 650 ° C 420: depositing the dome layer 430 with 100% trioxane: removing the wafer from the reactor 10 I2771396pin, 〇c/ol2 embodiment due to thermal and temperature control system limitations, dynamic The dynamic temperature variation plays an important role in the uniformity of deposition of the film on the surface of the substrate by chemical vapor deposition (CVD). It is generally preferred that the deposited film be as uniform as possible in thickness and elemental composition, but existing processes tend to produce a non-uniform film to improve the degree. This non-uniformity is always due to temperature variations across the surface of the substrate because the surface temperature of the substrate affects the deposition rate and the composition of the final film (the result mg fUm). Moreover, imperfect control of other process parameters, including gas flow rate and total pressure, is also believed to contribute to the inhomogeneity of the physical properties of the film. The pursuit of uniformity is often based on empirical adjustment of deposition conditions such as gas flow rate, substrate rotation speed, energy distribution of the heating element, etc., to achieve a desired film of uniform thickness. This is achieved by depositing a large number of films on the different substrates and at each substrate under different pre-selected set of deposition conditions. Then, the thickness variation of each film was measured and the results were analyzed to determine the conditions under which the thickness variation could be eliminated. However, it has been learned that an empirical process does not require a uniform temperature distribution throughout the process, or should be said to be a special reaction temperature 'set point' (set point / process effective time-average time change from temperature The resulting thickness variation. Therefore, the rule of thumb does not require uniform temperature across the substrate throughout the deposition process. In other words, because of the requirement for composition homogeneity in a solid that includes crossing the film surface and passing through the film thickness. Or at least control, ►pifl. Doc/012 caused controversy over compositional changes. This is because many films contain dopants, and the level of these dopants affects the electronic properties of the film. It also incurs other non-uniformities in the composition. The preferred embodiment provides a process for solving the above problems, and these processes can be used alone or preferably together. A process that affects the use of chemical precursors allows conventional precursors to provide film deposition at the same temperature to be processed in a mass transport limited growth regime. For a particular chemical precursor, the mass transfer specification is a temperature range in which the film deposition rate is temperature independent. The deposition rate is substantially unaffected by this small temperature change across the surface of the substrate in this temperature range, and these changes result in temperatures that are maintained at or near the mass transfer specification. This allows the film to be made more uniform than the conventional chemical precursors deposited at the same temperature, e.g., having a higher composition uniformity and thickness uniformity. This is because conventional precursors are deposited in mass transfer specification. Those skilled in the art will appreciate that the temperature range of the mass transfer specification can be determined by the particular precursor and reaction conditions and is illustrated by an Arrhenius diagram. In the case of the chemical precursor trisilane, the transition point from the temperature-dependent deposition rate to the temperature-independent deposition rate (traimUon pomt) is higher than that of decane or two. The conversion point of decane is much lower, as shown in Figure 10 for the Arrhenius diagram. The lower area to the transition point in the figure has 12 127713⁄4 846pifl. Doc/012 has a clearly upward linear slope, which means that the deposition of trioxane in the lower temperature range is highly correlated with temperature, so it is not in the mass transfer specification. For example, as shown in Figure 10, trioxane is at a flow rate of 25 standard cubic centimeters per minute (sccm) and a pressure of 40 Torr, and deposition at temperatures below 525 °C is not a mass transfer limitation (eg, in dynamic specifications). in). In contrast, the area above the transition point in the figure is almost flat, which means that the deposition of trioxane in this temperature range is temperature independent, so it is in the specification of mass transfer. For example, Figure 10 shows that trioxane deposition is clearly defined by mass transport at temperatures of about 620 ° C or above. It can be seen that the transition will occur in the Arrhenius diagram over a temperature range with a declining slope, meaning that the deposition of trioxane in this temperature range is virtually temperature-independent, but rather close to the mass transfer specification. For example, Figure 10 shows that the deposition quality of trioxane at a temperature of about 525 ° C or greater is defined by mass transport. It can be seen that the transition point may increase slightly at higher flow rates and slightly decrease at lower flow rates. For example, a transition point from deposition based on temperature to actual mass transfer limiting deposition has been verified to shift to higher temperatures as the trioxane flow rate increases. Thus, in contemporary manufacturing, for practical reasons (e.g., to maintain thermal budget retention of crystal characteristics, control of dopant profile, etc.), the use of trioxane can limit the deposition of mass transfer at a desired temperature. Various sand and bismuth-containing chemical precursors can be applied to the film deposition process disclosed herein to prepare ruthenium-containing, ruthenium-containing and alloy films containing ruthenium and osmium, such as sand shovel (SiGe' does not mean, etc. Stoichiometric) membrane. These chemistry 13 ►pifl. Doc/012 The precursor may also be used in combination with a carbon source to prepare an alloy film, such as a sand germanium carbon (SiGeC, here not meant to be stoichiometric) alloy film. Suitable for use in the present invention. The ruthenium chemical precursor comprises a higher-order non-halogenated hydride of ruthenium, especially a decane of the formula SinH2n+2, wherein n zz 2-6. Unique examples include dioxane (H3SiSiH3), trioxane (H3SiSiH2SiH3) and tetraoxane (HeSiHJiHAHD. Trioxane (also written as Sl3H8) is best used to achieve a balance between volatility and activity. Deposition under substantial or near mass transfer definition is preferred (but not necessary) for deposition of tantalum. Suitable for use in urgent inventions, only preferred chemical precursors containing ruthenium include a molecular formula of GenH2n+2. Higher decane, where n = 2 to 3. The source of lanthanum in other arrangements may include (H3Ge)(GeH2)x(GeH3), where X = 0~2. A unique example includes dioxane (H3GeGeH3) , trioxane (H3GeGeH2GeH3) and tetraoxane (H3GeGeH2GeH2GeH3). In a preferred embodiment, the chemical precursor is used in combination with a carbon source. A preferred carbon source comprises silylmethane [( H3Si)4_xCRx], where X = 0~3, R = Η and/or D-configuration. Preferred mercapto methane includes dimethane, trimethane and tetramethane (X = 0~2), The best is tetrahydromethane. Additional preferred carbon sources include hydrocarbons such as Alkanes, ethane, propane, butane, etc., as well as carbon monoxide, carbon dioxide and hydrogen cyanide (HCN). These chemical precursors and carbon sources can be obtained from commercial sources or are familiar with this technology. Synthesized by a method known as a ruthenium film such as MC, SiNC or SiOCX 14 127713⁄4 46pifl. None of the doc/012 means unique iso-stoichiometry) has many uses in semiconductor manufacturing, for example as an etch stop layer, a hard mask and a passivation layer. It is best to deposit with a unique chemical precursor at a temperature consistent with the mass transfer specification. For any unique chemical precursor and reaction conditions, the mass transfer limit specification can be determined at different temperatures by empirically derived from the deposition data (Airhenius diagram). The Arrhenius plot of the best ruthenium precursor, trioxane, under special conditions was added as shown in Figure 1 above. In addition to using the preferred chemical precursors described herein (particularly trioxane) and selecting a temperature for the precursor in a mass transfer specification, the deposition with the first process preferably includes appropriate other deposition parameter options. 'Specially the gas flow rate. The selection of preferred gas flow rates in conjunction with mass transfer limiting specifications is known to produce highly uniform films at much higher deposition rates than sand yards. In order to be deposited with sand at temperatures in the power specification, the uniformity of the membrane is primarily controlled by the set point on the temperature controller and the (a smaller range) gas flow rate. In contrast, for depositions containing higher levels of decane at a temperature-limited specification, it is known that the set point on the abuse controller is opposite to the sensitivity of the gas flow rate control set point (sensiUWty). For example, raising the set point on the temperature controller with the deposition of trioxane at the temperature transfer specification will have a much smaller effect than the set point on the boost gas flow controller. The preferred final film is more uniform than the comparable film when performing the deposition described herein. In addition to replacing the higher decane with decane and 15 I2771^46pif, doc/〇, or replacing the higher decane with decane, the "control film" used for this is in the film of the invention in question. All meaningful views are made in substantially the same way, and each film deposition process is separately adjusted to account for the difference in sensitivity to temperature and gas flow rate control set points, respectively. More particularly when comparing different layers As a result, the thickness uniformity measured by the following standard was measured by using an optional diameter across the wafer and measuring the thickness of the deposited layer along the diameter of 49 points. (Exclusion zone) is not measured. Then, the thickness measurement of the 49 points (for example, ± 6 angstroms) is the sum of the maximum thickness measurement between the 49 points plus the minimum thickness measurement. The uniformity is here expressed as a percentage. It is better to know that the method of using the precursor described herein can result in an abnormally high deposition rate, and more surprisingly High uniformity and smoothness 〇 For example, a preferred polycrystalline germanium film made with trioxane has a higher deposition rate than the one prepared by the same temperature used for decane at trioxane. The film has a large uniformity. Similarly, the inventors have separately formed an amorphous silicon (abbreviated a-Si) layer and an epitaxial silicon (epi-Si) layer using Sanshi Xiyuan. The better uniformity is compared with the sediment layer of the sand courtyard. See Figures 15 to 18 and the corresponding description below. Similarly, a better ruthenium film is prepared with higher decane and the ruthenium film has a ratio The uniformity of the control film prepared by replacing the higher decane with decane is greater. Moreover, higher deposition rates can be obtained at lower reaction temperatures using the disclosed ruthenium and ruthenium sources. 16 ►pifl. Doc/012 Figure 11 shows a linear plot of the deposition rate versus the flow rate of trioxane (in some of the illustrations, SilcoreTM) at a deposition temperature of 600 °C and a pressure of 40 Torr. This linearity further indicates that the Sanshayuan deposition under these conditions is substantially or close to the mass transfer limit, and further indicates that it has a much lower nucleation time than the oxide. Figure 12 is a plot of the film thickness of the film deposited with trioxane under the same conditions (650 ° C, 40 Torr) and the measurement site (she), except that the deposition time is varied from 90 seconds to 15 seconds. . Figure 12 shows excellent film uniformity over a wide range of deposition times at a fixed three-sand flow rate. The results represent not only time-average but the nature of the precursor. The (nature) and selected conditions, and because those layers remain uniform regardless of thickness, the emissivity (or other temperature-dependent temperature control) effect does not change the uniformity. Figure 13 shows the use of trioxane and diborane (as a dopant precursor) at a deposition temperature of 600 °C, a pressure of 40 Torr, and a range of diborane flow rates (from 0 to 18 〇seem). Deposition rate map. Figure 13 shows that the deposition rate using trioxane is quite inconsistent with the flow rate of the dopant precursor. In the lower temperatures that are more appropriate to reduce thermal stability, the preferred temperature range tends to favor a unique chemical precursor. For lesser grade sand yards and higher level brothels, a lower chain-length increase rate is preferred for lower temperatures. Therefore, the preferred temperature range for dioxane deposition will tend to be higher than trioxane, and in turn tend to be relatively higher than tetrasane and the like. And decane has a similar trend. The preferred deposition temperature for the deposition of trisane is above about 35 CTC, more preferably above about 45 Qt, and 127 for 2 to minimize hydrogen content in the final film. In order to achieve close or mass transfer specifications, the temperature is preferably maintained above about 525 ° C, even above about 550 ° C, and most is about above 600 ° C. The process can be carried out at temperatures above 700 ° C, but is preferably at or below about 700 ° C. Therefore, the preferred temperature is in the range of from 450 ° C to about 700 ° C, and more preferably in the range of from 525 ° C to about 650 ° C. For any unique chemical precursor or mixture thereof, the optimum temperature range can be determined by general experimentation using the guidelines provided herein. It is known that the temperatures listed are preferably used for thermal CVD. The lower temperature is suitable for the plasma assisted deposition process, depending on the degree of incorporation of the acceptable acid for the application. The choice of deposition temperature may also depend in part on the crystallinity required for the deposited layer. For example, the predominant crystallinity 矽 can be from about 620 ° C to 80 〇. (: Deposition in the range, and this deposition is clearly in the mass transfer specification. It is better to carry out polycrystalline germanium deposition between 650 ° C and 750 ° C. Lower temperature can be used for amorphous germanium deposition, and the temperature is the most It is preferred to maintain at least substantially the mass transfer definition (e.g., preferably at a temperature above 525 ° C.) The epitaxial enthalpy is largely dependent on the purity of the surface on which the deposition takes place. That is, those skilled in the art can Cognizing a very clean single crystal surface, such as a previously deposited epitaxial layer or the upper surface of a single wafer, can be epitaxially deposited over a wide range of temperatures depending on flow rate, pressure, etc. Epitaxial deposition on a suitable surface is typically It can be held at 5 〇 (TC~1160 °C. It is best to use a lower temperature range of, for example, from about 500 ° C to about 750 t for consideration of the thermal budget. See Figures 15 to 18 and related articles below 18 lpifl. Doc/012 Compared to the use of sand and/or brothel-made control membranes, it is preferred to use, for example, higher decane and/or at temperatures effective to achieve higher deposition rates and/or more uniform membranes. Or a chemical precursor of higher decane. The deposition of these chemical precursors can be suitably carried out according to various vapor deposition methods known to those skilled in the art, and when modified chemical vapor deposition is performed according to the teachings herein. The technology can be used to maximize the benefits of the deposition process. The disclosed process can be suitably carried out by performing a chemical vapor deposition method including plasma-enhanced CVD or thermal chemical vapor deposition, and is used for containing or containing germanium. A feed gas of a composition of a chemical precursor deposits a ruthenium containing or ruthenium containing film on a substrate in the chemical vapor deposition chamber. In a preferred embodiment, the gas is comprised of a Sanshayuan and a sand-containing film is deposited. In another preferred embodiment, the gas is comprised of a higher decane and a higher decane and a SiGe film is deposited. A variety of suitable methods can be used to provide the feed gas to the chemical vapor deposition chamber. The experimental results described herein are treated with a horizontal gas stream in a chemical vapor deposition chamber, and the preferred chamber is a single wafer horizontal gas stream radiant heating reactor. Suitable reactors of this type are commercially available, and preferred models include the EpsilonTM series of single wafer epitaxial reactors commercially available from ASM, Inc. of Phoenix, Arizona, USA. The process described herein may also employ a reactor such as a showerhead arrangement to facilitate increased uniformity in an EpsilonTM chamber known to be distributed in a horizontal single-pass laminar gas flow. Particularly effective 19 I2771396pi, doc/012 increased deposition rate. The chemical precursor supplied to the chemical vapor deposition chamber at the temperature and pressure for deposition is preferably in the form of a feed gas or a compound of a feed gas. The total pressure in the chemical vapor deposition chamber is preferably about 〇. 〇〇1 T〇rr to a range of about 700 T rr, more preferably in the range of about 01 T rr to about 200 T rr, most preferably in the range of about 1 T rr to about 60 Torr. Inside. The partial pressure of each cerium-containing and/or cerium-containing chemical precursor is preferably in the range of from about 1 χ 10-6% to about 100% of the total pressure, more preferably in the range of about 1 〇 1 〇 _ 4 %. To the range of about 100% of the total pressure. If a carbon source is used, the effective partial pressure is preferably to provide a final cerium and/or a carbon content of about 2% or less of the cerium-containing film (about 10% or less for the single crystal material). Content), even more preferably a carbon content of about 10% or less (about 5% or less carbon content for a single crystal material), the percentage here being based on the weight of the total film weight. The feed body may also contain gases from other chemical precursors and carbon sources, such as an inert carrier gas. Exemplary carrier gases include helium, argon, helium and neon. Hydrogen is the preferred process carrier gas described herein, particularly for single crystal materials. Nitrogen can also be used for the deposition of polycrystalline germanium and amorphous dicing films. Other compounds may be present in the feed gas as desired. Preferably, the preferred gas is further composed of one or more compounds selected from the group consisting of decane, dioxane, tetraoxane, decane, dioxane, trisomid, nitrogen dichloride (nf3), A group of mon〇silyhnethane, dimethane, dimethane, tetramethane, and a dopant precursor. The tragic precursors include diborane and deuterated diborane (deuterated 20 127713⁄4 846pifl. Doc/012 diborane), phosphine and arsine. Silylphosphme [(H3Si)3_xPRx] and silyl arsine [(H3Si)3_xAsRx] are preferred sources of phosphorus and arsenic, where X = 〇 〜 2, RX =H and / or D-configuration. SbH3 and dimethyl indium (trimiumin (jium) are preferred sources of chain and indium, respectively. These dopants and dopant sources are, for example, doped with lanthanum, phosphorus, antimony, indium and arsenic, which are produced by the above method. Tantalum and tantalum carbon films are useful. The doping concentration of these materials during doping is preferably in the range of about 1 x 1014 to about 1 x 1022 atoms/cm 3 . The dopants can be combined with very low dopant sources. The concentration, for example, in hydrogen, is in a concentration range of from about 1 ppm to about 1% total weight. Then, depending on the concentration to be doped and the concentration of the dopant gas, the mass flow controller is passed through the mass flow controller at a set point in the range of about 10 to 200 sccm ( The mass flow controller) delivers the diluted mixture to the reactor. The source of dopants may also be passed to the reactor with further hydrazine/hydrazine/carbon source together in the carrier gas, as the flow rate is typically about The concentration of 20 standard liters (SLM) to about 180 SLM, so the concentration of dopants used in the conventional process will be small. In the process of depositing yttrium and yttrium containing membranes, the relevant partial pressure of chemical precursors (and carbon source, if any) can be protected Fixed, or can be modified to produce a graded film having a different number of turns and/or turns in the film thickness as a function of depth. The film thickness is preferably in the range of about 10 angstroms to 5000 angstroms. The elemental composition of the film can be varied in a stepwise and/or continuous fashion. The application contemplated by the prior art can vary the film thickness by varying the deposition time and/or gas flow rate. The fixed or fractionated compound 21 I2771396pifLd〇c/012 deposited for use in the method described herein has a fixed composition opposite the doped film across any plane (Plane) at any uniquely set thickness. The deposition of a film on a substrate, the meaning of "planar" here is undulating. The deposition of the film described herein is preferably about 50 angstroms per minute (A / mm. It is implemented at a rate or higher rate, and more preferably at a rate or higher. The final ruthenium-containing film is preferably selected from the group consisting of a ruthenium film, a ruthenium carbon film, a tantalum nitride film (SiN, not meant to be stoichiometric), a ruthenium oxide film (SiO, not meant to be stoichiometric), Niobium oxynitride film (SiON, does not mean equal stoichiometry), doped boron film, doped arsenic film, doped phosphorus film, and has a dielectric constant of about 2. Group of membranes of 2 or lower. A method of making a suitable low dielectric constant film is disclosed in U.S. Application Serial No. 09/993,024, filed on Nov. 13, 2001. The ruthenium-containing film may be amorphous, polycrystalline or Jiajing. It is known that Sanshayuan has an excellent effect on the improvement of deposition rate and the uniformity of crystallites. The preferred embodiment also provides another process for solving the above problem of uniformity. An example of this process is presented in Figure 3 and Example 39 and is described in more detail herein. The non-uniformity of the composition through the thickness in the deposited layer is especially believed to be due to changes in kinetics (relative to statics) in the surface temperature of the substrate. Chemical vapor deposition chambers typically require a temperature controller to provide a set of temperature control conditions to maintain the deposition process throughout the unique layer. This setpoint abuse is usually selected at the beginning of the process and maintained until the layer is completed. In the above discussion, in the past, the film thickness problem has been found by empirically coordinating deposition conditions such as gas flow rate, substrate rotation speed, and energy distribution of the heating element, to effectively effect the thickness effect of the average temperature change of time 22 and 1涊6-2. It is known that a temperature set point or a set of reaction conditions that more often affect temperature control results in a film of a first 5 angstrom to 1000 angstrom deposition that is fairly uniform in composition and thickness, but this film will continue to deposit with deposition. It becomes uneven and becomes uneven. While this result is not readily apparent, and the invention is not limited to the principle, but the emissivity and other characteristics of the substrate, which will vary with the deposition time to affect the temperature control system. Relatively speaking, this produces a temperature change that results in a change in composition and thickness. Regardless of the reason for the transition to less uniform deposition, it is known to use a layer-by-layer approach to fabricate films having better uniformity. As in the present embodiment, a set of empirically determined temperature set points, T2, T3, etc., are determined on a layer-by-layer basis. A single film with a single point of special function in an integrated circuit is broken into several layers in an empirically determined process and each layer determines the most desirable set point. Thus, temperature control changes due to the thickness of the film formation can be offset during deposition by the use of separately setpoints that are effectively performed. An empirical decision can be made by first depositing a first layer on each of the different workpieces using individual temperature set points, and then measuring the thickness and composition changes of the first layer on each workpiece to identify What is the set point of the most uniform layer? The target thickness of the layer can be varied to a desired thickness depending on the degree of uniformity desired for a particular application, such as from about 50 angstroms to about 1000 angstroms, and preferably from about 100 angstroms to about 700 angstroms. Next, a first layer is prepared on the identified set points on a plurality of workpieces as an empirically determined basis for the second set point T2. When Τι determines 23 127713⁄43⁄4^ . After doc/012 is set, a second layer is deposited on the first film of each workpiece with each temperature set point, and then the change in thickness and composition is measured to determine the second set point that results in the most uniform second layer. The thickness of the second layer described above may be varied to a desired thickness depending on the degree of uniformity desired for a particular application, such as from about 5 angstroms to about 1000 angstroms, and more preferably from about 100 angstroms to about 700 angstroms. The process can be terminated if the most desirable first and second layers form a multi-layer film of the desired thickness and uniformity. If a thicker film is required, the process can be continued, for example, preparing a set of workpieces having two layers deposited at the first two identification set points, T2, and then using the various temperature set points on the second layer of each workpiece. A third layer is deposited, followed by a change in thickness and composition to determine the third set point 3 that results in the most uniform third layer, and so on. The temperature set point as used herein serves as an example of a fixed temperature control change during a deposition process, but the empirical process by the above teachings can be varied during deposition. This empirical process can also be used to maintain fixed temperature control changes during other single film deposition processes, such as the temperature offset (offset) or PID coefficient of the PID controller. Process variables such as gas flow rate, partial pressure and gas composition are preferably varied as described above for discriminating temperature set points or during the same experiment to release the desired deposition conditions for each layer. It is best to use experimental design methods to determine the combination of multiple process variations and their uniformity or deposition rate. The experimental design method is well known, see Douglas C.  Montgomery, "Design and Analysis of Experiments,w 2nd Ed. , John Wiley and Sons, 1984. For a unique process, by these experimental design methods I2771l96plfl. Doc/012 to determine the uniformity of the layer and / or the effect and combination of various process changes in the deposition rate, it is best to confirm a set of batch-to-batch or wafer by computer-controlled automatic process Wafer-to-wafer consistency. The best process improvement is due to on-the-spot (8), stepwise or dynamic adjustment to the above process variations. It is known that empirical methods for coordinating process variations that individually improve the characteristics of the layers can improve the properties of the entire unitary or functional film regardless of the above principles. Therefore, the operation of this embodiment is not correct or incorrect according to the principle. The set point, T2, T3, T4, etc. have been determined, and the preferred embodiment can also be used to assemble a temperature controller to provide a single method of chemical vapor deposition chamber programmed with multiple temperature set points. A preferred process is performed by inputting a temperature set point to the temperature controller and introducing a first gas comprising a X/ζό composition into the chemical vapor deposition chamber, wherein Xi ranges from about 0 to about 100. A first layer of germanium is then deposited on a substrate in the cavity. Preferably, the process continues to input a temperature set point of eight to the temperature controller, and introduces a second gas containing χ2% of the second cerium-containing chemical precursor into the chemical vapor deposition chamber, and then on the first ruthenium layer. A second ruthenium containing layer is deposited to form a multilayer ruthenium containing film. The second ruthenium containing chemical precursor may be the same or different from the first ruthenium containing chemical precursor and is shown in Figure 3 and Example 39. The process can continue, for example, by inputting a temperature set point T3 to the temperature controller, and introducing a third cerium-containing chemical precursor Χ3% of the third gas into the chemical vapor deposition chamber, and then on the second ruthenium layer. A third ruthenium-containing layer or the like is deposited to produce a ruthenium-containing film as many layers as desired. 25 12 127711 - Preferred chemical precursors include the higher decane described herein to include conventional chemical precursors such as decane. Preferably, one of the first and second chemical precursors is at least selected from the group consisting of decane, dioxane, and trioxane. Preferably, at least one of the first, second and third gases is selected from the group consisting of a brothel, a second brothel, a second brothel, a nitrogen difluoride (nf3), a sandstone, a methane, a third a mixture of methane, tetramethane, and a mixture of dopant precursors. The content of each of the cerium-containing chemical precursors in the gas at any particular stage of the deposition process, such as XA, χ2%, χ3%, χ4%, etc., is in the range of from about 1x to about 100% by volume, preferably It is in the range of about lx 10 to about 100%. The preferred temperature of the substrate is about 350 ° C or higher, and more preferably the temperature is in the range of 450 ° C to about 700 ° C. The chemical vapor deposition chamber is preferably a single wafer horizontal gas flow reactor. Finally, the multilayer ruthenium-containing film is preferably selected from the group consisting of a rmcrodot, a ruthenium film, a ruthenium carbon film, a nitriding film, a silicon-oxygen film, a sand oxynitride film. (silicon-oxygen-nitrogen film), doped boron film, antimony-doped arsenic film, doped phosphor film, and have a dielectric constant of about 2. Group of membranes of 2 or lower. A method of using a suitable low dielectric constant film is disclosed in U.S. Application Serial No. 09/993,024, filed on Nov. 13, 2001. The process of the preferred embodiment can be carried out by depositing a multilayer film in a stepwise or continuous process. When the deposition is paused to adjust the temperature set point, it is preferred to also adjust the process parameters required for flow rate, partial pressure, and gas composition to produce a film having a variety of compositions. For example, the deposited film described above may have a homogeneous or uniform composition or a gradual or continuous change in composition. While on a pause of 26^7713⁄4 6pifl. The identity of the ruthenium containing chemical precursor may be modified during doc/012 and/or its gas content X#, X2%, X3%, X4%, etc. may be altered. In a preferred embodiment, the process may affect the growth of the graded germanium concentration layer by discontinuous or stepwise changes in the germanium concentration. A preferred way to achieve this is by providing a layer of germanium concentration on top of each other to provide discontinuity. Periodic superlattice (supedamce). Example 39 will be clarified in conjunction with Example 43 below. The entire "film" of the known embodiment is composed of a single structural film from its functional point of view in an integrated circuit, and typically has a similar composition throughout its thickness. Therefore, a similar composition for defining a single film formed by the above-described stepwise deposition process comprises a graded film in which the same composition has different concentrations at different points in the film thickness. Methods for determining film uniformity and deposition rate are well known. The deposition rate can be measured by measuring the average thickness of the film as a function of time and is several angstroms per minute (A/min. ) as a unit. The preferred deposition rate is about 20 A/min. Or higher, and a better deposition rate of about 50 A/min. Or higher, and the optimum deposition rate is about 100 "min· or higher. Suitable methods for measuring film thickness include the multiple-point ellipsometric method. Instruments for measuring film thickness are also well known and commercially available, and preferably include NanoSpec® series instruments from Nanometrics, Inc., Sunnyvale, California. The term "uniformity" as used herein to mean the uniformity of the deposited film is also used to represent thickness uniformity and composition uniformity. The uniformity of the film thickness is preferably measured by multi-point film thickness measurement, and then the intermediate thickness is determined, and then the multiple measurement averages different from the middle number are determined. In order to be able to compare, 27 12771 said pifl. Doc/012 The percentage non-uniformity is used to indicate the result. The preferred percentage non-uniformity is about 10% or less, and more preferably about 5% or less, and most preferably about 2% or less. The uniformity of composition is measured by electrical measurements (such as four-point probe), secondary ion mass spectrometry (SIMS), Rutherford backscattering spectroscopy (RBS), and spectroscopy. Spectroscopic ellipsometry and/or high resolution X-ray diffractometry (HR-XRD). Figure 14 shows the 1306 A/min. Laceford backscattering spectroscopy (RBS) of amorphous ruthenium film deposited with trioxane at deposition rate, 40 Torr pressure and 600 ° C deposition temperature [Elastic Rec〇1 Detecnon spectrum] ]. The solid line represents the raw material of the film, and the dotted line is a data simulation software RUMPTM with assuming a residual hydrogen concentration of 0. 5 at. Model under %. The raw data refers to the slight surface contamination from the absorbed hydrocarbons or water vapor, but the energy spectrum represents the concentration of hydrogen remaining in the membrane under the detection limit, which is equivalent to less than 0. . 2 at·% chlorine concentration. Figure 15 shows an X-ray diffraction pattern of a series of ruthenium films deposited with trioxane at 600 ° C, 650 ° C, 700 ° C and 750 ° C (from the bottom to the top of Figure 15 respectively). The X-ray diffraction pattern shows that the film deposited at 650 ° C is partially crystalline at 60 (the TC deposited film is amorphous), while the film deposited at 7 ° C and 75 ° C is incrementally Crystallization. Figure 16 shows a section of the film (intermediate layer) deposited at 750 ° C. 28 1277 1 ^46 pifl. Doc/012 Penetrating electron micrograph showing a considerable degree of film thickness and thinness in a polycrystalline film deposited with Sanshayuan. A selected area diffraction (SAD) pattern of a film (as shown in Figure 17) shows that there is no preferential orientation in the film, i.e., a polycrystalline film. Figure 18 is a scanning electron micrograph of a non-crystalline tantalum film profile deposited with trioxane at 600 ° C and 40 Torr. The film deposited on the curved substrate is not deep and has excellent conformality in the slit. In another preferred embodiment, higher order decane is also used in the low temperature low pressure chemical vapor deposition synthesis of a composition of tantalum nitride (SiN) material ranging from almost pure tantalum to Sl3N4. The nitrogen source preferably includes, for example, a chemical precursor of trisilylamine (also written as (H3Si)3N], ammonia, atomic nitrogen (nitrogen) and nitrogen trifluoride (NF3). Preferably, the atomic nitrogen is produced by a remote microwave radical generator. The amount of nitrogen source introduced into the chemical vapor deposition chamber associated with the higher decane is preferably selected to provide a higher level of uniformity than the control film made using decane instead of higher decane. In a preferred embodiment, the atomic nitrogen is introduced continuously and is not continuously introduced or pulsed into the trioxane as one or more pulses. As explained in the following examples, it is known that a higher film uniformity can be obtained by pulse introduction of higher decane, and a very thin and highly uniform tantalum nitride film can be obtained by batch chemical vapor deposition. The tantalum nitride film prepared in accordance with the embodiment has a preferred thickness in the range of from about 10 angstroms to about 300 angstroms, more preferably from about 15 angstroms to 150 angstroms. The use of these nitrogen sources as a chemical precursor and in combination with trioxane is particularly applicable to 29 1277139 08846pifl. Doc/012 does not have a very small amount of nitrogen-hydrogen bonds in the film deposited at low temperatures, and its deposition rate is much higher than that of conventional germanium sources such as decane. The same result can be obtained with other higher decane. When the deposition temperature exceeds 450 ° C, the hydrogen content is preferably less than 4 at. %, more preferably less than 2 at. % ‘best is less than 1 at·%. The above deposition is preferably carried out in a mass transfer limiting specification. In another embodiment, higher order decane may also be used in the low temperature low pressure chemical vapor deposition synthesis of a cerium oxide material and a cerium oxynitride material. Higher grades The advantages of the low temperature and local growth rate of Shixiyuan provide manufacturing advantages over the use of decane, especially under low pressure chemical vapor deposition. Oxygen sources may include ozone, oxygen, water, nitric 0Xide, hydrogen peroxide, and the same source of oxygen. The nitrogen source used to direct nitrogen into these materials includes trisalamine, ammonia, atomic nitrogen and nitrogen trifluoride as described above. These oxygen sources and nitrogen sources can be used in conjunction with each other, either in a non-joining step or in a combination comprising these processes. The above deposition is preferably carried out in a mass transfer limiting specification or close to a mass transfer limiting specification. The deposition with tridecylamine and trioxane is preferably carried out in the range of from about 350 ° C to about 750 ° C, more preferably from about 40 (TC to about 700 ° C, most preferably at about 450 ° C to Approximately 650 ° C. The deposition with nitrogen trifluoride and trioxane is preferably carried out in the range of from about 300 ° C to about 750 ° C, more preferably from about 350 ° C to about 700 ° C, most preferably From about 400 ° C to about 650 ° C. Although individual examples of oxides and oxynitrides have not been proposed, those skilled in the art will readily appreciate the principles disclosed herein, as well as the above-described layers of tantalum nitride and tantalum. Equivalently applied to the deposition of yttrium oxide. Similarly, the advantages of 30 I2771^46pi, doc/012, and the lower activation energy and lower temperature to achieve mass transfer are beneficial to vapor deposition, especially Chemical vapor deposition of various bismuth compounds. A preferred embodiment provides films for a variety of applications in the microelectronics industry. Preferably, the ruthenium containing film has a thickness non-uniformity of less than about 2% and a composition of less than about 2%. Uniformity. The films described herein can be used in a variety of applications, such as transistor gate electrodes. The layers are particularly useful for forming key component layers in integrated circuits, such as the accumulation of gate layers in transistors. Other examples include semiconductor layers in heterojunction bipolar transistors (abbreviated as HBT's). Processes for integrated circuits are well known to those skilled in the art. These integrated circuits can be coupled to computer systems by methods known to those skilled in the art, so a preferred embodiment is provided by one or more A computer system consisting of integrated circuits. Figure 1 is a diagram of a preferred manufacturing process step described herein. Step 100, forming a gate dielectric layer on a semiconductor substrate. If necessary, step 110 The surface of the dielectric layer. The ruthenium containing film, preferably including the flowing trioxane, is then deposited as described above in step 120. Next, if lateral signal transmission is desired, a metal layer may be deposited in step 130. On the germanium-containing film, then, in step 140, the gate electrode is patterned, and in step 150, the fabrication of the integrated circuit is continued. Figure 2 is in accordance with the process of Figure 1. A schematic diagram of a gate stack 200. A gate dielectric layer 210 is formed on a semiconductor substrate 220, an electrically doped germanium-containing film 230 is formed on the gate dielectric layer 210, and a non-essential layer is placed on the germanium-containing film 230. Metal layer 240, thereby forming a gate 31 1277139 1 08^46pifl. Doc/012 Stack 200. The laminate 200 is then patterned to form a gate electrode (not shown in the second _), and the fabrication of the integrated circuit continues. It is preferred that the gate dielectric layer 210 can comprise at least one high dielectric constant material and have a dielectric constant greater than 5, more preferably a dielectric constant greater than 1 。. Exemplary materials include aluminum oxide, lead oxide, and antimony oxide, and are preferably formed by atomic layer deposition (ALD) to form a pinhole free layer. The use of trioxane in or near the mass transfer limit, especially in combination with higher broths, facilitates compensating for the slow nucleation time of conventional tantalum deposited on such high dielectric constant materials. In another example, an epitaxial germanium-containing layer is deposited on a single crystal substrate and the fluid is trioxane. The tantalum layer and the heterogeneous epitaxial germanium, tantalum carbide and tantalum carbon layers can be deposited by the processes described herein. Another preferred embodiment provides an apparatus for depositing a ruthenium containing material on a surface. The apparatus includes a chemical vapor deposition chamber (CVD chamber), a vessel containing a triple sand chamber, and a feed line for operating the connecting conduit to the chemical vapor deposition chamber to cause the conduit to The passage of trioxane in the fJ chemical vapor deposition chamber, and a temperature controller disposed around the conduit and maintained at a temperature in the range of about 10 ° C to 70 ° C, preferably at 15 ° C to about 52 t Control the evaporation rate of trioxane. Examples of suitable temperature controllers include thermoelectric controllers (*) and/or liquid-filled jackets. The preferred chemical vapor deposition chamber is a single wafer horizontal gas flow reactor. The entire instrument may also include a manifold for operating the connection feed tube 32 12771 fear 46 pifl. Doc/012 line to control the passage of the conduit to the trioxane of the chemical vapor deposition chamber. Preferably, a heat source is disposed around the feed line and the gas line is heated to between about 35 ° C and 70 ° C, more preferably between about 40 ° C and 52 ° C, to avoid condensation at high gas flow rates. Further, trioxane is preferably introduced by bubbling a trioxane vapor by a carrier gas, preferably a temperature-controlled bubble in combination with a heated gas line for transporting trioxane. Examples The following examples were performed with the ASM EpsUon 2000TM horizontal airflow epitaxy reactor system and equipped with a Bernoulli wand wafer transfer system, pure-only load lock, non-sliding concave surface A non-slide concave susceptor, a preheating ring, an adjustable spot lamp, and a tunable gas mlet injector. The ruthenium containing and ruthenium containing precursors are supplied to the chamber in a feed line and may contain hydrogen and diborane dopants. Then 120 seeming 1% diborane (B2H6) in hydrogen was diluted in 2 slm of hydrogen, and 120 seem of the mixture was introduced into a reactor mixed with 20 slm of hydrogen and precursor, and in the example shown below The flow rate is deposited on a rotating substrate. The deposition rate was judged by a secondary ion mass spectrometer and an optical ellipsometer (Nanometnc) from the depth profile of oxygen and boron. Mm 1-4 According to Table 1, the ruthenium-containing film was deposited using trioxane as a chemical precursor. The deposition temperature is 70 (TC. 33 127713⁄4 846pifl.) for the mass transfer specification of trioxane. Doc/012 However, because the flow rate (under these special deposition conditions) is not suitable for providing a uniform film, the final film is not uniform but has a concave profile on the deposition profile (thinner, thicker edges). Table 1 No. Temperature re) Pressure (Torr) Flow Rate Setting 値 (seem) Precursor Base Deposition Profile 1 700 40 50 Si, H« SiCh Concave 2 700 40 45 SiA Si〇, Concave 3 700 40 15 Si, Η, Si〇 , concave 4 700 40 25 Si, Η, Si〇, concave example 5~15 According to the parameters shown in Table 2, using trioxane and decane as chemical precursors and diborane as dopant to deposit yttrium-containing amorphous film . Diluted 120 seem of 1% diborane (B2H6) in hydrogen to 2 slm of hydrogen, and introduced 120 seem of the mixture into a reactor mixed with 20 slm of hydrogen, trioxane and decane, wherein the flow rates of trioxane and decane The conditions are shown in Table 2. These results show that the use of trioxane at a preset temperature results in a higher deposition rate than the use of decane, even in the case where the trioxane flow rate is lower than the decane flow rate. 34 I27713?46pifl,oc/012 Table 2 No. Temperature (°C) Pressure (Torr) Flow rate see (seem) Precursor Base Deposition rate (A/min. 5C 650 40 50 SiH4 _ Si09 46 6C 650 40 50 SiH4 Si <10〇〉 68 7 650 40 50 Si.H, Si <l〇〇> 462 8C 600 40 50 SiH4 Si02 19 9C 600 40 50 SiH4 Si <l〇〇> 9 10 600 40 20 Si, H8 [TsiO. 359 11 600 40 15 SiA Si <l〇〇> 181 12C 550 760 25 SiH4 Si〇2 <1 13C 550 40 50 SiH4 Si〇2 7 14 550 40 30 SiA —Si〇? 287 15C 550 40 50 SiH4 Si〇2 2 Examples 16 to 19 According to the parameters shown in Table 3, tritane and decane were used as chemical precursors to deposit the ruthenium-containing film. The deposition time can be adjusted to give each film an average thickness of about 500 angstroms. The average thickness was then measured using an ellipsometric measure of Nanometnc and these numbers were assigned by the deposition time to determine the deposition rate. The film non-uniformity can be judged by the 49-point thickness map of the film thickness. The results show that the use of trioxane instead of decane at the specified temperature results in a more uniform film at very high deposition rates. It can be at 550 ° C, but it is more attractive at 600 ° C. 35 /012 /012 Table 3 No. Precursor Temperature (°C) % Inhomogeneity 1 SiH4 600 5.93 2 Si, Η, a 600 0.83 3 SiH4 550 8.5 ^ 4 Si, H8 a 550 7.31 ~~ Sink. Product rate _example 20~38

A ruthenium film was obtained by substituting a mixture of 80% trioxane and 20% dioxane instead of trioxane alone and a mixture of 80% decane and 20% dioxane instead of decane alone to repeat Examples 1-19. This gives a higher deposition rate than using only trioxane and decane. Example 39

Refer to the procedure shown in Figure 3 and provide a ruthenium film by the following discontinuous periodic superlattice growth. In step 300, a 矽 <100> substrate is prepared, and the substrate is placed in a reactor under high flow of ultrapure hydrogen, and then a d-magic fluorinated gas (HF) is applied. Clean to remove native oxide. Rotate at 60 rpm under a high flow of hydrogen (to remove any contaminants on the substrate surface) when the wafer is heated to 9 °C. Then, the wafer was cooled and stabilized at 700 ° C, and a arsenic-doped buffer layer having a thickness of about 300 angstroms was grown with tri-sand and trisilylarsine under mass transfer conditions. In step 310, the set point is adjusted to 600 ° c' to cool the wafer temperature by cooling under a stream of hydrogen. In step 320, a first stage ruthenium superlattice is deposited with 98% dioxane and 2% dioxane. In step 330, 36 127711. Marine 85% trioxane and 15% dioxane are deposited in a second stage ruthenium superlattice. Under a stream of hydrogen, in step 340, the set point temperature is lowered by 3 ° C and the wafer is allowed to stabilize for 30 seconds. Further in step 350, a third stage ruthenium superlattice is deposited with 75% trioxane and 25% dioxane. Under a stream of hydrogen, in step 360, the 3 °C set point temperature is lowered and the wafer is allowed to stabilize for 30 seconds. Further in step 370, a fourth stage ruthenium superlattice is deposited with 65% trioxane and 35% dioxane. In step 380, 85°/ is used. Trioxane, 12% dioxane, 2% diborane and 1% dimethane methane were deposited in a fifth stage boron-doped and carbon-doped germanium superlattice. Under a stream of hydrogen, in step 390, the reactor was simmered for 30 seconds. In a further step 400, a sixth stage ruthenium superlattice is deposited with 90% trioxane and dioxane. Under the hydrogen flow, in step 410, the set point is increased to 650 ° C, and the relative energy of the emitter bank is slightly adjusted to maximize the wafer center uniformity (within_wafer uniformity) of the growing stone roof cap layer. . Wafer stabilization is then provided for 30 seconds. The top cover layer is deposited with 100% trioxane in step 420. Finally, in step 430, the wafer is removed from the reactor and the next wafer is processed. Example 40 A ruthenium-containing film having an average thickness of 1,038 angstroms was deposited using trioxane and decane as chemical precursors at a deposition temperature of 650 ° C and a pressure of 40 Torr. The flow injector set point has been empirically adjusted to the usual method for a prior range of operations. The final ruthenium film with a percent non-uniformity of 0.37% (8 angstrom range) was measured by scanning with a 49 point linear dimension excluding the 6 cm edge. Figure 4 shows the film thickness and the measured site. fl.doc/012 diagram. Example 41 (Comparative Edition) A ruthenium-containing film was deposited on a cerium oxide (SiO 2 ) substrate (without a nucleation layer) at 60 (TC temperature) using decane and decane as precursors. The atomic force microscopy (AFM) was measured at a scan area of 10 μm x 10 μm and was 226 angstroms. The sand raft film was revealed to be island-type deposition by scanning electron microscopy (SEM). (Island-type deposition) pyramidal, faceted grain, as shown in Figures 5 and 6. Scanning electron micrographs are shown in Example 41 at 600°. C deposits a ruthenium-containing film, but replaces decane and decane with trioxane and decane as precursors. The surface roughness of the final ruthenium film is measured by atomic force microscopy (AFM) at a scan area of 10 μm×10 μm. The enamel film reveals a much more uniform surface via a scanning electron microscope (SEM), such as the scanning electron micrographs shown in Figures 7 and 8 (respectively with Fig. 5 and Fig. 6, respectively). Have the same put Magnification and tilt angle.) Examples 43 to 63 A series of ruthenium-containing films were deposited on a cerium oxide (SiO 2 ) substrate (without a nucleation layer) using trioxane and decane at a pressure of 40 Torr. The fourth example is fixed at 77 seem (hydrogen carrier, bubble). The decane flow rate (10% decane, 90% hydrogen) and the deposition temperature are variable as shown in Table 4. The final ruthenium concentration of the ruthenium film (atomic %) and thickness were determined by Raspford 38 c/012 1277 ll.d. Backscattering spectroscopy (RBS), and surface roughness was determined by atomic force microscopy (AFM). The results in Table 4 show A film of high uniformity can be prepared over a range of temperatures and flow rates, and particularly within a range of concentrations. Table 4 No. Temperature CC) decane flow (seem) % 锗 thickness (A) Sink rate (A/min. Roughness 0 (A) 43 450 25 5.0 34* 8.5 3.2 44 450 50 7.5 34* 11 4.1 45 450 100 * 11 59* 15 3.7 46 450 100 11 53* 13 nd 47 500 25 6.0 190 63 7.8 48 500 50 10 230 77 9.1 49 500 100 13.5 290 97 8.3 50 500 100 13.5 380* 127 7.2 51 550 25 6.0 630 315 5.2 52 550 50 9 .5 670 335 13.6 53 550 100 14 300 450 12.1 54 550 100 14 1016 508 9.4 55 600 25 7.0 1160 580 8.1 56 600 50 13 1230 615 25.7 57 600 100 19 1685 843 31.8 58 650 25 11 630 630 23.3 59 650 50 17 800 800 31.5 60 650 100 27 1050 1050 50.2 61 700 25 11 680 680 18.1 62 700 50 18 835 835 37.8 63 700 100 31 960 960 , 44.9 > represents the thickness of the nd measured by optical technique: undetermined 39 127713⁄43⁄4 46pifl.doc/012 Examples 64-78 In Table 5, a series of ruthenium is deposited on the primary oxide layer of ruthenium <100> using trioxane and ammonia (Example 64-77) or decane and ammonia (Example 78). membrane. The carrier gas flow rate is 30 slm and the ammonia gas flow rate is 7 slm. Table 5 shows not only the deposition rate and refractive index ("RI") measured by the final tantalum nitride (SiN) film, but also the atomic ratio of silicon to nitrogen. That is, "Si/N") and hydrogen content (ie "%H"). Table 5 No. Pressure (Torr) Temperature (V) Carrier Source/Flow Rate (seem) Deposition Rate (A/min.) Si/N %H RI 64 20 625 n2 Trioxane / 20 124 0.85 4 2.074 65 20 725 n2矽/20 149 0.85 4 2.034 66 20 725 n2 Trioxane / 80 585 0.95 4 2.182 67 20 725 h2 Trioxane / 80 611 1.0 2.2 2.266 68 20 775 n2 Trioxane / 20 158 0.88 4 2.010 69 20 775 h2 Trioxane / 20 117 0.88 3 1.999 70 20 775 n2 Trioxane / 40 308 0.85 4 2.053 71 20 775 n2 Trioxane / 80 582 0.88 4 2.101 72 20 775 h2 Trioxane / 80 600 0.88 3.5 2.146 73 20 775 n2 Trioxane / 160 1050 0.88 4 2.141 74 20 775 h2 trioxane / 160 1283 0.92 3.5 2.281 75 20 775 n2 trioxane / 80 346 nd nd 2.006 76 100 775 n2 trioxane / 160 589 nd nd 2.028 77 100 775 h2 trioxane / 160 244 nd nd 2.012 78 100 775 n2 decane / 40 208 nd nd 2.007 nd : undetermined atomic ratio of ruthenium to nitrogen ("Si/N") and hydrogen content by Russell 40 127713⁄4; 46pifl.doc/012 backscattering Spectroscopic (RBS) determination. Figure 19 shows the Rutherford backscattering spectrum (2 MeV He++) of a tantalum nitride sample deposited with trioxane at 775 °C and 20 T rr. Figure 20 shows the elastic recoil detection spectrum obtained by recoil detection (ERD). These figures show the raw data and the simulation (smuilat1〇n) obtained from the RUMP manufacturing model that can be quantified as enthalpy, nitrogen, and hydrogen concentration. The simulation map represents that the film has a stoichiometric ratio of about Si45N51H4. Figure 20, the Laceford backscattering spectral elastic recoil detection spectrum (RBS ERD spectrum) also reveals that hydrogen is uniformly distributed throughout the membrane. Examples 79 to 82 use a mixture of trioxane and atomic nitrogen on the primary oxide layer of the ruthenium <1〇〇> substrate to deposit a series of ruthenium-containing materials. A commercially available 800 watt microwave radiation generates a radical radical generator (MRG) to produce the atomic nitrogen ' and supplies it to the chemical vapor deposition chamber. Using a nitrogen carrier gas at a flow rate of 5 slm (1 sim in Example 82), the trioxane is supplied to the chemical vapor deposition chamber via a bubbler together with the atomic nitrogen, and its deposition temperature is as shown in Table 6. Shown. The introduction of trioxane to the chamber is not as in the case of Example 79. Continuously, as in the case of 8 to 82, it is pulsed. Pulse introduction was carried out by continuously introducing atomic nitrogen and pulse-introducing trioxane at intervals of about 1 minute and 30 seconds. Under the above flow conditions, each trioxane pulse lasted for about 6 seconds. Each final tantalum nitride film has a stoichiometric ratio ranging from approximately S43N54 56H3 i . Table 6 shows the thickness, refractive index, and hydrogen level in the final tantalum nitride film. The tantalum nitride film of Example 79 is inconsistent because the center is significantly thicker than the edge of the edge 41 oc/012 I277l^46pifl.d and the measured refractive index of the transmembrane surface also changes (at the center above the edge) ). Examples 80 to 82 using pulsed processes improve uniformity. A uniform film can also be obtained by a continuous process that increases the atomic nitrogen flow rate and/or reduces the flow rate of the three chambers. Table 6 Numbering Process Deposition Temperature (°C) Refractive Index %H Center Edge 79 Continuous 650 869 J 510 1.97-2.2 2 80 Pulse 650 324 268 1.98 2 81 Pulse 600 635 655 1.96 3 82 Pulse 650 1115 1174 2.02 0.7 Section 83 In general, as described in Examples 80-82, a continuous tantalum nitride film having a thickness of about 18 angstroms was deposited using a remotely generated atomic nitrogen and a single six second pulsed trioxane at 650 ° C under a pressure of 3 Torr. This film was coated with an epoxy and profiled to take a transmission electron microscopy (TEM) image, such as a transmission electron micrograph shown in Fig. 9. It can be found that the interface between the film and the substrate has no native oxide. Examples 84 to 87 A series of epitaxial ruthenium films were deposited on a cleaned ruthenium <100> substrate using trioxane at a deposition temperature of 40 Torr at a deposition temperature and a deposition rate as shown in Table 7. As shown in Table 7, Z-mm値 obtained from the Laceford backscattering channel spectrum can be used to produce a high-quality epitaxial film. 42 127713⁄4 46pifl.doc/012 Table 7 Numbered deposition temperature fc) Deposition rate (A/min.) χ -min(%) 84 650 47 2.7 85 650 50 3.1 86 600 145 2.9 87 650 460 3.2 Although the invention has been The preferred embodiments are disclosed above, but are not intended to limit the present invention. Any one skilled in the art can make some modifications and refinements without departing from the spirit and scope of the present invention. The scope defined in the appended patent application shall prevail. 43

Claims (1)

丨 8M6pifl.doc/012 Pickup, Patent Application Range: 1. An improved deposition process for a semiconductor film by depositing a highly uniform germanium-containing material on a surface, the steps comprising: providing a cavity with a substrate, the substrate Having a controlled temperature for the deposition using trioxane vapor, the controlled temperature being selected to establish a mass transfer limiting condition; directing a gas comprising trioxane into the chamber, wherein a flow rate of the gas is selected To improve the deposition uniformity of the deposition of the trioxane relative to the decane; and to deposit a ruthenium-containing film on the substrate. 2. The improved deposition process for a semiconductor film according to claim 1, wherein the ruthenium-containing film is epitaxial. </ RTI> 3. The improved sink process of the semiconductor film of claim 1, wherein the ruthenium-containing film is polycrystalline. 4. The improved deposition process for a semiconductor film according to claim 1, wherein the controlled temperature is in the range of from 450 ° C to 750 ° C. ❿ 5. The improved deposition process of the semiconductor film of claim 4, wherein the controlled temperature is in the range of from 550 ° C to 650 ° C. 6. The improved deposition process for a semiconductor film according to claim 1, wherein the ruthenium-containing film is deposited on the substrate at a rate of about 50 angstroms per minute or more. 7. The modified sink film of the semiconductor film of claim 1, wherein the deposition rate of the ruthenium-containing film on the substrate is about 100 angstroms or more per minute. 8. The improved deposition process of a semiconductor film according to claim 1, wherein the amorphous ruthenium-containing film has a thickness non-uniformity of about 5% or less across the substrate. 9. The improved deposition process of a semiconductor film according to claim 1, wherein the amorphous ruthenium-containing film has a thickness non-uniformity of about 1% or less across the substrate. 10. The improved deposition process for a semiconductor film according to claim 1, wherein the gas further comprises one or more selected from the group consisting of decane, brothel, brothel, brothel, difluorination. A compound of the group of nitrogen, sandstone, squash, triterpene, tetramethane and a dopant precursor. 11. The improved deposition process for a semiconductor film according to claim 1, wherein the gas further comprises dioxane. 12. The improved deposition process for a semiconductor film according to claim 1, wherein the cavity is a single wafer horizontal gas flow reactor. 13. The improved deposition process for a semiconductor thin film according to claim 1, wherein the ruthenium-containing film is selected from the group consisting of a minute shrinkage point, a tantalum film, a tantalum carbon film, and a tantalum nitride layer. a film, a hafnium oxide film, a hafnium oxynitride film, a doped boron film, a doped arsenic film, a doped phosphor film, an doped indium film, a doped germanium film, and having a dielectric constant of about 2.2 or A group of lower membranes. 14. The improved deposition process of a semiconductor film according to claim 1, wherein the ruthenium containing film is ruthenium and the substrate is a material having a high dielectric constant. 45 127713⁄4 46 pifl.doc/012 15. The improved deposition process of the semiconductor film of claim 1, further comprising patterning the ruthenium containing film to form a transistor gate. 16. A process for depositing a ruthenium-containing material on a surface, comprising: providing a chemical vapor deposition chamber configured with a substrate; directing a gas comprising trioxane into the chemical vapor deposition chamber; and _ above A ruthenium-containing film was deposited on the substrate at a temperature of 525 ° C. The ruthenium-containing film had a higher degree of uniformity at a higher deposition rate than a control film made with decane instead of trioxane. 17. A process for depositing a ruthenium-containing material as described in claim 16 wherein the substrate is maintained at a temperature of about 550 ° C or higher. 18. A process for depositing a ruthenium-containing material as described in claim 16 wherein the substrate is maintained at a temperature of about 620 ° C or higher. 19. A process for depositing a ruthenium-containing material as described in claim 16 wherein the substrate is maintained at a temperature of about ▽(8) or higher. 20. The process of depositing a ruthenium-containing material as described in claim 16 wherein the substrate is maintained at a temperature ranging from 450 ° C to 700 ° C. 21. A process for depositing a ruthenium-containing material as described in claim 16 wherein the substrate is maintained at a temperature ranging from 525 ° C to 650 ° C. 22. A process for depositing a ruthenium-containing material as described in claim 16 wherein the ruthenium-containing film is deposited at a rate of about 50 angstroms per minute or more. 46 I2771396pifLd〇c/〇i2 23. A process for depositing a ruthenium-containing material as described in claim 16 wherein the ruthenium-containing film is deposited at a rate of about 100 angstroms per minute or more. 24. The process of depositing a ruthenium-containing material on a surface as described in claim 16 wherein the gas further comprises one or more selected from the group consisting of decane, dioxin, sputum, and nitrogen trifluoride. a compound of a group of sand sands, two sand methane, three stone methane, four methane and one dopant precursor. 25. The process of depositing a ruthenium-containing material on a surface as described in claim 16 wherein the gas further comprises dioxane. 26. The process of depositing a germanium-containing material on a surface as described in claim 16 wherein the chemical vapor deposition chamber is a single wafer horizontal gas flow reactor. 27. A process for depositing a ruthenium-containing material as described in claim 16 wherein the ruthenium-containing film has a thickness non-uniformity of about 5% or less. 28. The process of depositing a ruthenium-containing material on a surface as described in claim 16 wherein the ruthenium-containing film has a thickness non-uniformity of about 1% or less. 29. The process for depositing a ruthenium-containing material on a surface as described in claim 16 wherein the ruthenium-containing film is selected from the group consisting of a minute crater, a ruthenium film, a ruthenium carbon film, and a nitridation layer. a ruthenium film, a ruthenium-oxygen film, a ruthenium-oxygen-nitrogen film, a doped boron film, a doped arsenic film, an doped indium film, a doped yttrium film, a doped phosphor film, and a dielectric A group of films having a constant of about 2.2 or less. 30. The process of depositing a ruthenium-containing material as described in claim 16 wherein the ruthenium-containing film is ruthenium and the substrate is a material having a high dielectric constant of 127713⁄4 46 pifl.doc/012. 31. The process of depositing a ruthenium-containing material on a surface as described in claim 16 wherein the ruthenium-containing film is epitaxial. 32. The process of depositing a ruthenium-containing material on a surface as described in claim 16 wherein the ruthenium-containing film is polycrystalline. 33. The process of depositing a ruthenium-containing material on a surface as described in claim 16 wherein the ruthenium-containing film is amorphous. 34. The process of depositing a germanium-containing material as described in claim 16 of the patent application, further comprising patterning to form a transistor gate. 35. A compounded ruthenium-containing film having a thickness unevenness of about 5% or less on an integrated circuit, and a ruthenium-containing film across the compound in any of the set films One of the depths of about 2% or less constitutes unevenness. 36. A ruthenium-containing film as described in claim 35, comprising a transistor gate. 37. The ruthenium-containing film according to claim 35, which has a thickness unevenness of about 1% or less. 38. A ruthenium-containing film as described in claim 35, including a ruthenium film. 39. A ruthenium-containing film as described in claim 35, comprising a polycrystalline material. 40. A ruthenium-containing film as described in claim 35, comprising an amorphous material. 41. A process for depositing a layer of material on a surface, comprising: 48 12771 涊 6 pifl.doc/012 providing a chemical vapor deposition chamber configured with a substrate; directing a higher decane and a higher decane a gas into the chemical vapor deposition chamber; and depositing a tantalum film on the substrate. 42. The process of depositing a bismuth material as described in claim 41, wherein the higher decane is selected from the group consisting of dioxane, trioxane and tetraoxane. 43. The process of depositing a bismuth material as described in claim 41, wherein the higher decane is selected from the group consisting of dioxane, trioxane and tetraoxane. 44. The process of depositing a bismuth material as described in claim 41, wherein the higher decane is trioxane and the higher decane is a wrong yard. 45. The process of depositing a tantalum material as described in claim 41, wherein depositing the tantalum film is in a temperature range from 475 ° C to 700 ° C. 46. The process of depositing a tantalum material as described in claim 41, wherein the rate of depositing the tantalum film is about 50 angstroms or more per minute. 47. The process of depositing a tantalum material as described in claim 41, wherein the rate of depositing the tantalum film is about 100 angstroms or more per minute. 48. The process of depositing a tantalum material on a surface as described in claim 41, wherein the gas further comprises one or more selected from the group consisting of: 矽49 &gt;Pifl.doc/012 methane, diterpenes a compound of the group of methane, triterpene methane, tetramethane, and a dopant precursor. 49. The process of depositing a tantalum material on a surface as described in claim 41, wherein the chemical vapor deposition chamber is a single wafer horizontal gas flow reactor. 50. A process for depositing a tantalum material as described in claim 41, wherein the tantalum film has a thickness non-uniformity of 5% or less. 51. The process of depositing a bismuth material as described in claim 41, wherein the ruthenium film has superior uniformity to a control film made by substituting the higher decane with decane. 52. The process of depositing a bismuth material as described in claim 41, wherein the ruthenium film has superior uniformity to a control film made by substituting the higher decane with decane. 53. The process of depositing a tantalum material as described in claim 41, further comprising patterning to form a transistor gate. 54. A ruthenium film having a thickness unevenness of about 5% or less and a compositional unevenness of about 2% or less on an integrated circuit. 55. The ruthenium film as described in claim 54 of the patent application includes a transistor gate. 56. The ruthenium film of claim 54, wherein the ruthenium film has a thickness unevenness of about 1% or less, and a composition unevenness of about 2% or less. 50 I2771^46pifld〇c/〇i2 57. A process for depositing a ruthenium-containing material on a surface, comprising: providing a chemical vapor deposition chamber configured with a substrate, the chemical vapor deposition chamber being assembled with a temperature controller In order to program a plurality of temperature control variables in a single method; input a temperature control variable or even the temperature controller; and direct a first gas comprising a first cerium-containing chemical precursor of XA to the chemical vapor deposition chamber In the body, wherein Χι is in the range of 1χ1〇·4 to about 1〇〇; depositing a first ruthenium-containing film on the substrate; inputting a temperature control variable τ2 to the temperature controller; guiding includes an X2% a second gas containing a ruthenium chemical precursor into the chemical vapor deposition chamber, wherein Χ2 is in the range of lx 10.4 to about 100' and the second ruthenium containing chemical precursor and the first a ruthenium containing chemical precursor is one of the same and different; and depositing a second ruthenium containing film on the first ruthenium containing film to form a thickness unevenness of about 5% or less and about 2% Or a lower compositional unevenness A multilayer containing ruthenium film. 58. The process for depositing a ruthenium-containing material on the surface as described in claim 57, wherein the temperature control variables 1 and T2 are temperature control settings. 59. The process for depositing a eucalyptus-containing material on a surface as described in claim 57, further comprising:: inputting a temperature control variable Τ3 to the temperature controller; guiding a third bismuth-containing chemical precursor including a bismuth a third gas of the substance is introduced into the chemical vapor deposition chamber; and 51 丨pifl.doc/012 deposits a third ruthenium-containing film on the second ruthenium-containing film. 60. The process of depositing a ruthenium-containing material as described in claim 57, wherein one of the first ruthenium-containing chemical precursor and the second ruthenium-containing chemical precursor is at least selected from the group consisting of decane, A group of dioxane and trioxane. 61. The process of depositing a ruthenium-containing material as described in claim 57, wherein one of the first gas and the second gas comprises at least one or more selected from the group consisting of decane, A compound of the group of decane, trioxane, nitrogen trifluoride, monomethane, methane, trimethylmethane, tetramethane, and a dopant precursor. 62. A process for depositing a ruthenium-containing material on a surface as described in claim 57, wherein the substrate has a temperature of about 350 ° C or higher. 63. A process for depositing a ruthenium-containing material as described in claim 57, wherein the substrate has a temperature range of from about 475 ° C to 7 (8) t. 64. The process of depositing a germanium-containing material on a surface as described in claim 57, wherein the chemical vapor deposition chamber is a single wafer horizontal gas flow reactor. · 65. The process for depositing a ruthenium-containing material on a surface as described in claim 57, wherein the multi-layer ruthenium film is selected from the group consisting of a minute crater, a ruthenium film, a ruthenium carbon film, and a a tantalum nitride film, a germanium-oxygen film, a germanium-oxygen-nitrogen film, a doped boron film, a doped arsenic film, an doped indium film, a doped germanium film, a doped phosphor film, and a An amorphous film, a polycrystalline film, an epitaxial film, and a group of films having a dielectric constant of about 2.2 or less. 66. An apparatus for depositing a cerium-containing material on a surface, comprising: 52 I2771^896pifid〇c/0i2 a chemical vapor deposition chamber; a conduit containing trioxane; a feed line for operatively connecting the a conduit to the chemical vapor deposition chamber to pass trioxane from the conduit to the chemical vapor deposition chamber; and a temperature controller disposed around the conduit and maintained at about 10 ° C to 70 ° C At a temperature, the evaporation rate of trioxane is controlled. 67. An apparatus for depositing a ruthenium-containing material on a surface as described in claim 66, further comprising a manifold for operatively connecting the feed line to control the conduit to the chemical vapor deposition chamber The passage of trioxane. 68. An apparatus for depositing a cerium-containing material on a surface as described in claim 66, wherein the temperature controller comprises one of a heating blanket, a heating liquid, and a heating lamp. 69. An apparatus for depositing a ruthenium-containing material on a surface as described in claim 66, wherein the chemical vapor deposition chamber is a single wafer horizontal gas flow reactor. 70. An apparatus for depositing a ruthenium-containing material on a surface as described in claim 66, wherein the conduit is a foamer equipped with a carrier gas source, wherein the carrier gas is selected from the group consisting of hydrogen and helium. Groups of helium, argon, helium and nitrogen. 71. An apparatus for depositing a ruthenium-containing material on a surface as described in claim 70, wherein the carrier gas comprises hydrogen. 72. An apparatus for depositing a ruthenium-containing material on a surface as described in claim 70, further comprising a heat source surrounding the feed line and maintaining 53 ►pifl.doc/012 35 ° C to 70 ° C The temperature between them to reduce the condensation of trioxane in the feed line. 73. An apparatus for depositing a ruthenium-containing material on a surface as described in claim 66, wherein the temperature controller is maintained at a temperature between 15 ° C and 52 ° C. 74. The improved deposition process for a semiconductor film according to claim 15, wherein the ruthenium-containing film is deposited on a gate dielectric material having a dielectric constant greater than 5. 75. The improved deposition process for a semiconductor film according to claim 74, wherein the gate dielectric material comprises one of alumina, oxidized, and zirconia. The improved deposition process of the semiconductor film of claim 1, wherein the ruthenium-containing film comprises ruthenium oxide. The modified deposition process of the semiconductor film of claim 1, wherein the ruthenium-containing film comprises ruthenium oxynitride. 78. The improved deposition process of a semiconductor film according to claim 1, wherein the germanium-containing film comprises tantalum nitride. _ 79. The improved deposition process of the semiconductor film of claim 1, wherein the gas further comprises a nitrogen source. 80. The improved deposition process for a semiconductor thin film according to claim 79, wherein the nitrogen source is selected from the group consisting of nitrogen trifluoride, tridecylamine, atomic nitrogen and ammonia. 81. The improved deposition process for a semiconductor thin film according to claim 80, wherein the nitrogen source comprises atomic nitrogen. 54 1277 1 ^46 pifl.doc/012 82. An improved deposition process for a semiconductor film as described in claim 80, wherein the trioxane is pulsed. 83. The improved deposition process for a semiconductor film according to claim 80, wherein the ruthenium-containing film is a nitrid sand film having a thickness in the range of 10 angstroms to 300 angstroms. 55 ic/012 柒, designated representative map: (1) The representative representative of the case is: ( ). (2) The symbolic representation of the symbol of the representative figure is as follows: 捌 If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention.