TWI282125B - Method for curing low dielectric constant film by electron beam - Google Patents

Abstract

A method for depositing a low dielectric constant film on a substrate. The method includes a low dielectric constant film comprising silicon, carbon, oxygen and hydrogen in a chemical vapor deposition chamber. The method further includes exposing the low dielectric constant film to an electron beam at conditions sufficient to increase the hardness of the low dielectric constant film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of integrated circuits, and more particularly to a process for depositing a dielectric layer on a substrate. [Prior Art] Since the introduction of the integrated circuit for the first time decades ago, the size of the integrated circuit has been greatly reduced. Since then, the size of the integrated circuit has basically followed the principle of reducing the size by half every two years (generally called "Moore's Law"). In this case, it also represents the number of components on a wafer every two years. Will double. Today's wafer fabs are routinely capable of producing 〇13 microns, or even ι·ιm. Future wafer fabrication facilities will be able to produce smaller dimensions. As component sizes continue to shrink, the need for low-k films is increasing in the market as the need to further reduce capacitive coupling between adjacent metal lines to reduce component size on integrated circuits. In particular, the k value is below 4.0 < Low-k insulating layer The insulating layer of the low-k value insulating layer includes spin-coating, earth-doped bismuth glass (USG), fluorine-doped bismuth glass (FSG) ), and the collection of four gas, are generally available on the market. One way to effectively reduce the value of k is to introduce holes into the film. As a result, the mechanical strength (i.e., hardness) of the low-k film is made low, which in turn makes it difficult to integrate the film into the component manufacturing process. At present, plasma post-treatment is used to improve the mechanical strength of the low-k film, but the plasma treatment will cause an increase in the k value. Therefore, there is a need for a method for improving the mechanical strength of a low-k thin 1282125 film without increasing the value of k. SUMMARY OF THE INVENTION The present invention is generally directed to a method of depositing a low force > Φ deposition constant film on a substrate. The method includes depositing a low dielectric constant film comprising germanium, carbon, oxygen and hydrogen in a chemical vapor deposition process. The inventors of the present invention comprise exposing the low dielectric constant film to an electron beam sufficient to increase the hardness of the low dielectric film. [Embodiment] Nouns The detailed description of the present invention is provided below. The items used here

I W is defined as follows. As for the nouns used in the scope of application for patents, Sun Hanzhi knows the technical staff of the present invention to provide a maximum hardness, splitting threshold and power in an ultra-low dielectric constant film according to the broadest scope of the invention. Significant and unexpected improvements. In one embodiment, a film comprising ruthenium, carbon, oxygen and hydrogen is deposited on a substrate surface under conditions sufficient to form an ultra-low dielectric constant (k value #2.5) film. Thereafter, the ultra low force constant film is further post-treated with an electron beam. In accordance with one or more embodiments of the present invention, electron beam ("e-beam") processing can be utilized to improve properties such as mechanical properties, thermal stability, dielectric constant, etch selectivity, and resistance to isotropic stripping (eg, Membrane properties such as a non-crosslinked polymer that can be easily etched by a downstream plasma stripping process, and copper diffusion barrier properties. It is generally believed that at least one aspect, "e-beam The treatment system, 'two' by the negative decrosslinking of the film to provide such improvement (that is, the general phase of 1282125 to crosslink the carbon bonds), by the Young's coefficient (Y〇ung, s letter "e- The beam treatment is preferably carried out by removing hydrogen bonds to enhance and increase the surface hardness and moduius on the film. It is generally believed that, at least in most cases, this objective can be achieved with little change in the overall composition of the film. One or more embodiments of the present invention - the first step of fabricating a low dielectric layer is deposited by a CVD deposition process (described in detail below) whose low-k dielectric layer can comprise a predetermined porosity. Under normal circumstances, such deposits will be very soft and contain sub- MetastaMe specie. When such CVD deposits are thermally hardened, the metastable species will be driven away, and the layer will shrink - such a layer U is about 2.6. By exposing the film to _ The plasma hardening process in the electric environment reduces the time required to spend on the thermosetting process. However, since the effect of the plasma hardening process is limited to the surface of the film, the effect of this process is limited. According to a second embodiment of the present invention, the second step of fabricating the low-k dielectric layer is to perform an "e-beam" process on the CVD deposited layer (including simultaneously heating the film layer), thereby converting the film layer into one: And a highly crosslinked film layer. Finally, in accordance with this embodiment of the invention, in the third step of selectively performing the fabrication of the low-k dielectric layer, the filament over-treated film layer is heat-hardened. "6_beam" treatment of the (10) deposit layer can strengthen the film structure, (4) and can drive away the metastable species to avoid shrinkage of the film. Manufacturing a low-k + electric layer method containing Jane, ft, and carbon The example uses a <a ring compound containing more than 4 kinds of organic bases as its = drive. Examples also include mixed use - or a variety of organic bottomed cyclic compounds and / or a variety of organic ruthenium-based acyclic compounds. In a 5 1282125 aspect, an organic - ruthenium-based cyclic compound. The oral substance, an organic 矽-based non-reading compound, and the -hydrocarbon system and the oxidizing gas are reacted under conditions to form a low dielectric constant film layer having a k value of less than 2.5 t. The hard-bottomed acyclic compound includes at least a 1-carbon bond. The organic-exclusive acyclic compound includes, for example, but not limited to, a hard-nitrogen bond or a-fragment-oxygen bond. The hydrocarbon may be linear or cyclic, and may include a carbon-carbon double bond or a carbon-carbon triple bond. According to one or more embodiments of the present invention, if at least the organic germanium gas contains oxygen, then An oxidizing gas may not be needed. The CVD film layer contains a network of oxime-oxo-oxime rings which are crosslinked with one or more linear organic compounds. Because of this cross-linking structure, @ can produce a reactive stable network with a large gap between the ring structures, so the deposited film layer has a high porosity. The ultra-low dielectric constant film layer is generally produced by mixing one or more precursor gases, including an organic ruthenium ring compound, a fatty compound, a hydrocarbon, and an oxidizing compound. The organofluorene ring compound may include a cyclic structure having one or more deuterium atoms, and the cyclic structure may further contain one or more oxygen atoms. Commercially available organofluorene cyclic compounds include a ring having a phase spacing < oxime, an oxygen atom and one or two alkyl rings bonded to the ruthenium atoms. For example, the organofluorene ring compound may include one or more of the following compounds: (-SiH2CH2-)3-(cyclic) (-SiH(CH3)-0-)4-(cyclic) (-SiH(CH3)2 -0-) 4-(cyclic) 1,3,5-trimethylcyclohexane 1,3,5,7-tetramethyltetradecaneoctane (TMCTS) octamethyltetradecaneoctane (OMCTS) (-SiH(CH3)-0-)5-(cyclic) (-SiH2-CH2-SiH2-0)2-(cyclic) (-Si(CH3)2-0-)3-(cyclic) 1282125 1,3 ,5,7,9-pentamethylpentacyclononane ring-1,3,5,7-tetrahydro-2,6-dioxo-4,8-octane 1,3,5-triazine- The 2,4,6-trioxane fatty compound includes a linear or branched (ie, acyclic) organic hydrazine compound having one or more deuterium atoms, one or an atom; a chain or a branched The organic cerium compound has at least one unsaturated carbon bond and may further comprise oxygen. Commercially available fatty organic hydrazine compounds include hydrazine-free organic decanolides and organic decanolides of one or more germanium atoms. For example, the fatty organic compound includes one or more of the following compounds: a plurality of carbons and the straight. The oxygen atom between the junction atoms may be decyl decane dimethyl dimethyl decane trimethyl decane diethoxy methoxy decane (DEMS) dimethyl dimethoxy decane (DMDMOS) dimethyl dimethoxy decane Ethyl nonanedioxanyl methane bis(methyl decyl) methane 1,2-dimethyl decyl ethane 1,2-bis(methyl decyl) ethane CH3-SiH3 (CH3)2-SiH2

(CH3)rSiH CH3-SiH-(0-CH2-CH3)2 (CH3-0)2-Si-(CH3)2 (CH3)2-Si-(0-CH3)2 CH3-CH2-SiH3

SiH3-CH2-SiH3 CH3-SiH2-CH2-SiH2-CH3

SiH3-CH2-CH2-SiH3 CH3-SiH2-CH2-CH2-SiH2-CH3 1282125 2,2-xylylalkylpropane SiH3-C(CH3)2-SiH3 1,3-dimethyldioxane CH3- SiH2-0-SiH2-CH3 1,1,3,3-tetramethyldioxane (TMDSO) (CH3)2-SiH-0-SiH-(CH3)2 hexamethyldioxane (CH3) ) 3-Si-0-Si_(CH3)3 1,3-bis(methyl decyl methylene) dioxane (SiH3-CH2-SiH2-)rO bis(1-methyldixy oxyalkyl)methane (CH3-SiHrO-SiH2-)2-CH2 2,2-bis(1-methyldioxaoxyalkyl)propane (CH3-SiH2.〇-SiH2-)rC(CH3)2 hexamethoxydioxane (CH3-0)3-Si-0-Si-(CH3-0)3 t diethylformane (C2H5)2-SiH2 propylformane C3H7-SiH3 vinylmethyl decane CH2=CH-SiH2- CH3 1,1,2,2-tetramethyldioxane (TMDSO) (CH3)2-SiH-SiH-(CH3)2 hexamethyldioxane (CH3)3-Si-Si-(CH3)3 1, 1,2,2,3,3-hexamethyltrioxane (CH3)2-SiH-Si(CH3)2-SiH-(CH3)2 - 1,1,2,3,3-pentamethyltrioxane (CH3)rSiH-Si(CH3)-SiH-(CH3)2 dimethyl dimethyl dimethyl hydride CH3-SiH2-(CH2)2-SiH2-CH3 dimethyl dimethyl hydrazine alkyl propane CH3-SiH- ( CH2)3-SiH-CH3 % Tetramethyldimethyl dimethyl alkyl ethane (C H3) 2-SiH-(CH2)2-SiH-(CH3)2 Tetramethyldimethylhydrazinealkylpropane (CH3)rSiH-(CH2)3-Si.(CH3)2 Number of adjacent carbon atoms of hydrocarbons It is between 1 and 20. The hydrocarbon may include a phase-positive carbon atom bonded by a single bond, a double bond or a triple bond. For example, the organic compound may include olefins and alkynes having about 20 carbon atoms, such as ethylene, propylene, ethylene, butadiene, tert-butylethylene, 1,1,3,3 - 8 1282125 Methyl·(methyl)propionic acid (MMA) and tert-butyltetramethylbutylbenzene, tert-butyl ether carboxymethyl ether. The organic compound further comprises an organic compound having a carbon chloride composition having one or more unsaturated carbon-carbon bonds, such as a carbon-carbon double bond, a carbon-carbon triple bond or an aromatic group. . For example, the organic telluride having one or more unsaturated carbon-carbon bonded hydrocarbons may comprise one or more of the following components: Ethyl methyl methacrylate Trimethylsulfonium acetylene 1-(trimethylsulfonium)-1,3-butadiene trimethylsulfonium cyclopentadienyl trimethylhydrazine ethyl acetate di-tert-butoxydiethoxy decane CH2=CH -SiH2-CH3 (CH3-0)2-Si(CH3)-CH=CH2

(CH3)3Si-C^CH (CH3)3Si-HC=CH-HC=CH2 (CH3)3Si-C5H5 (CH3)3Si-0(C=0)CH3 ((CH3)3(O0))2-Si - ((C = 0) (CH3) 3) 2 In one embodiment, the one or more organic telluride systems having one or more unsaturated carbon-carbon bonded hydrocarbons and one or more oxidizing gases The reaction is carried to the surface of the substrate under conditions sufficient to form a low dielectric constant deposited layer on the surface of the substrate. In another embodiment, one or more organic tellurides and one or more fatty hydrocarbon systems are reacted with one or more oxidizing gases and are conditions sufficient to form a low dielectric constant deposited layer on the surface of the substrate. The lower is transferred to the surface of the substrate. The fatty hydrocarbon may comprise from 1 to 20 adjacent carbon atoms. The carbon atoms of the carbon nanotubes may be bonded to each other by a combination of a single bond, a double bond, and a triple bond of any of the three bonds. Preferably, the fatty hydrocarbon comprises at least one unsaturated carbon-carbon bond. For example, the fatty hydrocarbon may include cigarettes, cigarettes, and diene having a carbon number of 2 to 20, such as acetamidine, propylene, isobutyl, acetylene, propyne, ethyl. Acetylene, i, 3-butane, isoprene, 2,3-dimethyl-1,3-butadiene and pentane. In another embodiment, the invention includes a significant but unexpected low dielectric constant film layer comprising ruthenium, oxygen and carbon by one or more compounds having at least one cyclic group and Or a plurality of organic tellurides and a selectively added oxidizing gas are mixed under conditions sufficient to form a network of pretreated layers. In one aspect of the invention, one or more compounds having at least one cyclic group and one or more organic telluride systems are reacted with a sufficient amount of oxidizing gas to form a low dielectric constant film layer on the semiconductor substrate. . The film is deposited by plasma in a process chamber capable of performing chemical vapor deposition (CVD). The plasma can be generated by RF, high frequency RF, dual frequency, two phase RF, or any conventional or undiscovered plasma generation technique. After depositing the film layer, the film layer is hardened by an electron beam to remove the hanging organic groups, such as the ring-shaped base ring of the organic compound incorporated into the film layer during deposition. The hardening step is capable of supplying energy to the network of layers to volatilize and remove at least a portion of the cyclic groups in the network of the layer. In most cases, the hardness of the hardened film is at least doubled, even up to 6 times, far better than the hardness of the film that has not been hardened. The dielectric constant (k) of the electron beam-hardened film layer is unexpectedly greatly reduced, and the hardness is increased, which is an effect that cannot be achieved by the conventional hardening technique. Typically, the hardened film layer has a dielectric constant (k) of about 2.5 or less, preferably 2.2 or 2 2 10 1282125 or less, and a hardness of more than 0.6 GPa. As for the one or more compounds having at least one cyclic group, "cyclic group" means a cyclic structure herein. The ring structure may include structures as few as three atoms. The atom can be carbon, helium, nitrogen, oxygen, fluorine, and combinations thereof. The cyclic group can include one or more single bonds, double bonds, triple bonds, and combinations thereof. For example, a cyclic group can include one or more aromatic groups, phenyl, cyclohexane, cyclohexadiene, and combinations thereof. The cyclic group may also be a bicyclic ring or a tricyclic ring. Further, the cyclic group is preferably bonded to a straight chain or branched functional group. The linear or branched functional group preferably contains a monoalkyl group or an ethylene alkyl group and has a carbon number of from 1 to 20. The linear or branched functional group may also contain an oxygen atom such as a C-, an ether, and an ester. Some examples of compounds having at least one cyclic group include terpene (oxime), ethenylcyclohexane (VCH), and phenylacetate. Some of the above precursors contain oxygen atoms and therefore do not require the addition of an additional oxidizing agent. However, in any of the embodiments described, one or more oxidizing gases may be required. In embodiments in which one or more oxidizing gases or liquids are desired, it may include oxygen, ozone, nitrous oxide, carbon monoxide, carbon dioxide, water, hydrogen peroxide, an organic compound containing oxygen atoms, or a combination thereof. . In an embodiment, the oxidizing gas is oxygen. In another embodiment, the oxidizing gas is ozone. When ozone is used as the oxidizing gas, an ozone converter converts about 6% to 20% (oxygen weight ratio) of a gas in a source gas, typically about 15%, into ozone, and the rest is still oxygen. However, the ozone concentration can be adjusted (ie, increased or decreased) depending on the amount of ozone required and the ozone converter used. The one or more oxidizing gas systems are added to the anti-11 1282125 gas mixture to increase reactivity. And it became a carbon content in the children's layer. The deposition of the ultra low dielectric constant film layer may be continuously or discontinuously deposited in a separate deposition chamber. Alternatively, the film layer may be deposited continuously in two or more deposition chambers, for example, in a ProducerTM process chamber combination provided by Applied Materials. The deposited layer has a carbon content of about 5 to 3 atomic percent (except hydrogen atoms), preferably about 5 to 20 atomic percent. The carbon content of the deposited layer means that the atomic analysis of the film structure shows that it does not contain a significant amount of non-bonded hydrocarbon. This carbon content is expressed as a percentage of carbon atoms in the deposited layer and excludes hydrogen atoms which are difficult to quantify. For example, a film having an average of one dream atom, one oxygen source +, one carbon atom, and two hydrogen atoms has a carbon content of about 20 atomic percent (one carbon atom or five carbon atoms per 5 atoms). It is about 33 atomic percent (except for hydrogen atoms, which contains a hydrogen atom). The atom (the film layer can be deposited in any process chamber that can be subjected to chemical vapor deposition (CVD). Referring to Figure i, the edge shows an upright cross-section with parallel cvd _. The process chamber 1〇 includes a high The vacuum zone 15 and a gas knife dispersion g 1 1 'child gas dispersion manifold 1 1 have a plurality of small holes (not shown), a cylinder, a knife to the substrate, and the substrate is placed on the substrate. The substrate support plate or the crystal 2 is mounted on a support column 13 to connect the crystal holder U to a lift motor 14. The lift motor 4 can be used for the crystal holder 12 liters are asked to go to a place where the seedlings are placed, lowered, or lowered to a lower substrate loading position, so that the 'substrate is supported on the upper surface of the crystal holder 12' can be controlled to A movement between the lower loading/unloading position of 12 1282125 and the processing position of a higher adjacent gas dispersion '& 11'. When it is located at a higher processing position, one, "color, 1 7 is far more %" The crystal seat 12 and the substrate are read around. The gas system introduced into the gas dispersion manifold 1 1 is radially dispersed to disperse the surface of the material. A vacuum pump 32 with a regulating valve can be controlled. The process chamber 1 passes through the flow rate of the exhaust gas flowing out of the manifold 24. If necessary, the deposition gas and the carrier gas pass through the gas line 18 into the mixing system 1 9, and then enter the gas dispersion manifold 丨i. The process gas supply line 18 includes (i) a safety shut-off port (not shown) for automatically or manually shutting down the process gas flow to the process chamber; and (ii) a flow control device (not shown) for measuring The gas flow rate through the process gas supply line 18. When the process requires the use of toxic gases, each of the private gas supply lines 18 will be provided with several safety shut-off valves. During deposition, one or more cyclic organic deuteration The mixture of the substance and the one or more fatty compounds is reacted with an oxidizing gas to form an ultra-low-k film layer on the substrate. The cyclic organic telluride may be combined with at least one fatty organic compound and at least one fat. Pulsed hydrocarbon mixture. For example, the mixture comprises from about 5% by volume to about 80% by volume of one or more cyclic organic tellurides, from 5% by volume to about 15% ( 5% by volume) one or more lipids a fatty organic telluride, and 5% (% by volume) to about 45 ° / (% by volume) of one or more fatty hydrocarbons. The mixture may also comprise from about 5% (% by volume) to about 20% ( One or more oxidizing gases. Alternatively, the mixture may comprise from about 45°/(% by volume) to about 60°/〇 (% by volume) of one or more cyclic organic tellurides, 5 % (% by volume) to about 10 ° / 〇 (% by volume) of one or more fatty organic tellurides, and 5% (% by volume) to about 35% (% by volume) of one or more fats 13 1282125 Hydrocarbonation The one or more cyclic organic tellurides are typically introduced into the mixing system 19 at a flow rate of about 1 Torr to 1 Torr, preferably at a flow rate of about 520 seem. The one or more fatty organic tellurides are typically introduced into the mixing system 19 at a flow rate of from about 100 to about 1.0 seem, preferably at a flow rate of about 60 Oseem. The one or more fatty hydrocarbons are typically introduced into the mixing system 19 at a flow rate of from about 100 to 1,000 sccm, preferably at a flow rate of about 2,000 sccm. The flow rate of the oxygen-containing gas is generally between about 100 and 6,000 seem, preferably about 1, 〇〇〇 seem. The one or more organic tellurides having one or more unsaturated carbon-carbon bonded hydrocarbon compositions are typically introduced into the mixing system 19 at a flow rate of from about 100 to 1,000 seem. Preferably, the cyclic organic telluride is 1,3,5,7-tetramethyltetranoncyclooctane (TMCTS), octamethyltetradecaneoctane (OMCTS) or a mixture thereof; The organic telluride is trimethylformane, 1,1,3,3-tetramethyldioxane or a mixture thereof; the fatty hydrocarbon is preferably ethylene. In another aspect, the fatty hydrocarbon comprises one or more metastable precursors. The one or more metastable precursors are introduced in an amount from about 1 〇 〇 to 5,0 0 〇 s c c m . Preferably, the metastable precursor is a tert-butyl ether. The deposition process can be a thermal process or a plasma enhanced process. In a plasma enhancement process, an RF energy is applied from the RF power supply 25 to the gas dispersion manifold 11 to produce a plasma adjacent the substrate. Alternatively, RF energy can be supplied to the crystal holder 12. The RF energy in the deposition chamber can be either cyclic or pulsed to reduce heating of the substrate and promote porosity of the deposited layer. The plasma energy density of a 300 mm substrate is between about 14 watts/flat 14 1282125 cm2 and 2.8 watts/cm2, which is equivalent to an RF power of ι〇瓦 to 2000 watts. Preferably, the RF power is between 300 watts and 1700 watts. The power supply 25 can supply a single frequency RF energy from 〇·〇ι MHz to 300 MHz. Alternatively, the RF power supply 25 can also transmit a mixing frequency to enhance the decomposition process of the reactive species entering the high vacuum zone 15. In one embodiment, the hybrid frequency is a low frequency of about 12 kHz to a same frequency of about 1 3 56 MHz. In another embodiment, the low frequency is between about 4 kHz and about 14 MHz; and the high frequency is between about 20 MHz and about 100 MHz. In another embodiment, the low frequency is between about 300 Hz and about 1 kHz kHz; and the high frequency system is between about 5 MHz and about 50 MHz. / When the product is accumulated, the substrate temperature is maintained at _2 〇. (between 3 and about 500 ° C, preferably maintained at about 1 Torr. 〇 to about 400 ° C. The deposition pressure is generally between about 托 5 Torr to about 20 Torr, preferably between about 2 Torr to about 8 Torr. / The rate of efflux is typically between about 5,000 person/minute and about 20 000 A/minute. If it is desired that the oxidizing gas system dissociate at a remote location, a microwave chamber 28 can be used. In order to provide energy between about 5 watts and 6 watts of watts to the oxidizing gas before the gas enters the process chamber. The additional microwave energy prevents the organic bismuth compound from being excessively decomposed before reacting with the oxidizing gas. When a microwave energy is applied to an oxidizing gas, it is preferred to use a gas dispersion plate having individual channels for organic telluride and oxidizing gas. Typically, 'any process chamber liner, dispersion Manifolds, crystal holders 12, and various other reactor hardware are made of materials such as aluminum or anodized aluminum. One example of such a CVD chamber is detailed in the United States of America. Patent No. 5, 〇〇〇, 113, entitled "a Thermal CVD/PECVD and 15 1282125 in-situ Multi-Step Planarized Process, and to the assignee of the present application, Applied Materials, the entire disclosure of which is incorporated herein by reference. 14. A gas mixing system 19, and an RF power supply 25. The system controller 34 controls the activity of the CVD process chamber via a hard disk drive, a floppy disk drive, and a car rack. The card holder includes a single Motherboard computer (SBC), analog and digital I/O boards' interface boards and stepper motor control boards. System controllers conform to the dimensions of the motherboard, clip housing and connectors as defined by the Versa Modular Europeans (VME) specification And the VME standard also defines that the structure of the bus bar is a 16-bit data bus and a 24-bit address bus. The pre-processing and method for forming a pre-processed layer of the present invention is not limited to any particular one. Apparatus or any particular plasma excitation method. The above CVD is also described solely for the purpose of illustrating the invention, and those skilled in the art will recognize that an ECR plasma CVD apparatus such as an ECR plasma CVD apparatus can be used. CVD device or The present invention is embodied in a CVD apparatus similar to that of the apparatus. Further, the above-described design, heating design, energy connection design, and the like of the substrate holder are equivalently changed without departing from the spirit of the invention. In the embodiment, when a low dielectric constant film layer is deposited, the film layer is preferably an electron beam. Treatment (e·beam). The electron beam treatment is typically treated with a dose of 1 to 20 electron volts and a dose of 5 〇 to 2 〇〇 microcoulomb/cm 2 (::/(10)”. The electron beam is processed to form a beam of light = to about 45 minutes at about 45 ° C for about 15 minutes, for example about 2 minutes. Preferably, the electron beam treatment (e-beam) is carried out at about 400 ° C for about 2 minutes. 16 1282125 • 5 mA and 5 氩 argon and hydrogen. In one aspect, the conditions of the electron beam include 4.5 kV, i μο/em 2, and 400 ° C. There may be a presence during electron beam processing. Although any type of electron beam apparatus may be used, an exemplary apparatus is an ebk chamber, Applied Materials, Inc. product. Treating the low dielectric constant film layer with an electron beam after deposition of the low dielectric constant film layer will cause at least a portion of the organic groups on the film layer to be volatilized to form pores in the film layer. The organic group which can be volatilized is derived from the organic composition of the foregoing precursor, for example, an organic telluride having one or more unsaturated carbon-carbon bonded hydrocarbons or the said aliphatic hydrocarbon. It is believed that the formation of pores in the film layer reduces the dielectric constant of the film layer. Preferably, the film layer is not deposited at temperatures above 15 Torr because it is believed that high temperatures will render the film layer incapable of incorporating a sufficient amount of volatile organic groups. The details and process of the exemplary e-beam chamber are detailed below. The substrate is transferred by vacuum braking or by vacuum in a vacuum environment (i.e., without a vacuum brake). Figure 2 shows a beam chamber 2 in accordance with one embodiment of the present invention. The chamber 2 includes a vacuum chamber 220, a large surface area cathode 222, a target plate 230 located in the field-free zone 238, and a gate 226 between the target plate 230 and the large surface area cathode 222. The e-beam chamber 200 further includes a high potential insulator 224, which can connect the gate 226 and the large surface area cathode 222, a cathode which can cover the insulator 228 outside the vacuum to 220, and can control the pressure in the vacuum chamber 220. The modulating leak valve 232, an adjustable high potential power source 229 coupled to the large surface area cathode 222, and an adjustable low potential power source 23 1 coupled to the gate 226 are isolated. The process chamber may also include a lamp (not shown) that illuminates and heats the substrate, whereby the temperature of the process chamber is 17 1282125. The light can be located under the target & 23〇. Because the material is located in the real-life aid τ V, ^, the soil heating is "isolated, so the substrate can be irradiated by radiation: the part. The light is extinguished and extinguished." The substrate will be radiated away from the heat source. The aging material is gradually cooled by the surface of the environment. During the entire process, the two materials can be simultaneously heated by the lamp and irradiated with electron beam radiation. For example, according to the invention - the embodiment, the infrared quartz lamp is opened Until the substrate temperature reaches the process operating temperature. After that, the lamp is turned off or on in different operating cycles to control the wafer temperature. The substrate is continuously irradiated with electrons until a sufficient dose is accumulated and the substrate has been processed. This technique can harden a thick layer on a substrate in 10 minutes. According to another embodiment of the invention, the substrate is not cured using an infrared lamp. Such an embodiment of the invention is illuminated and heated by an electron beam. In this case, the current product and the current potential (energy = current * potential) are much larger than the energy radiated from the substrate, so the substrate is heated by an electron beam. Further according to the present invention In an embodiment, the substrate is cooled by a cooling plate. This will keep the substrate temperature close to the predetermined temperature. The substrate to be exposed to the electron beam is placed on the target plate 230 during operation. The vacuum chamber 220 is brought close to atmospheric pressure. Under the pressure, the vacuum is started until the pressure is between 1 Torr and about 200 mTorr. The pressure of the vacuum chamber 220 is precisely controlled by the adjustable speed leak valve 232, which can control the pressure to about 〇·1. The electron beam system is generated at a sufficiently high potential which is generated by applying a potential to the large surface area cathode 222 with a high potential power source 229. The potential may range from -500 volts to about 30,000 volts or more. The potential power source 2 2 9 may be a berta η 18 1282125 type #1 05-30R ' manufactured by Bertan of Hickville, New York or a Spellman type #SL30N-1200X258 manufactured by Spellman High Voltage Electronics Corp. The power source 2 3 1 can supply a potential to the gate 2 2 6 , and the potential on the gate 226 is positive relative to the large surface area cathode 222. This potential is used to control the emission from the large surface area cathode 222. The adjustable low potential power supply 231 can be an Acopian type #150 PT21 power supply manufactured by the Acopian of Easton, Pennsylvania. To initiate the emission of the electron beam, the % free zone between the gate 226 and the target plate 23 is free. The gas in 8 must be freed, which may be due to natural gamma rays. It is also possible to artificially initiate electron beam emission in a vacuum chamber with a high potential spark gap. Once initially free, positive ions 342 (as shown in Figure 3) It is attracted to the gate 226 by a slightly negative potential (i.e., a potential applied to the gate 226 between 〇 and _2 volts). These positive ions are accelerated toward the large surface area cathode 222 (by the high potential applied to the large surface area cathode 222) through the acceleration field region 236 (between the large surface area cathode 222 and the gate 226). Upon impact on the large surface area cathode 222, these energetic ions produce electrons 344 which are accelerated toward the gate 226 in the other direction. A portion of this type of electrons flies in the direction of the vertical cathode surface and strikes the gate 226, but most of the electrons 344 pass through the gate 226 and fly to the target plate 230. Gate 226 is preferably disposed at a shorter distance from the mean free path of electrons emitted by large surface area cathode 222. That is, the gate 226 is preferably located within a distance of 4 mm from the large surface area cathode 222. Since the distance between the gate 2 26 and the large surface area cathode 2 2 2 is very short, little or no electrons are freed in the acceleration field region 2 3 6 between the gate 226 and the large surface area cathode 222 19 1282125. come out. In conventional gas discharge devices, electrons create more positive ions in the acceleration field. These positive ions are attracted to the large surface area cathode 222, causing more electrons to be emitted. This discharge phenomenon easily becomes an unstable high-potential discharge that cannot be controlled. However, in accordance with an embodiment of the invention, electrons 342 generated outside of gate 226 can be controlled (repulsed or attracted) by the potential applied to gate 226. In other words, the electron emission phenomenon can be continuously controlled by changing the potential on the gate 226. Alternatively, the electronic launch is controlled by an adjustable leak valve 232 that is configured to increase or decrease the number of molecules located in the free zone between the target plate 23 and the large surface area cathode 222. Applying a positive potential on the gate 226 (i.e., when the gate potential exceeds any positive ion species energy in the space between the target plate 230 and the large surface area cathode 222) can completely interrupt electron emission. Figure 4 shows an e-beam chamber 2 具有 having a feedback control circuit 400. In some applications, a constant electron current with different electron beam energies is provided. For example, the upper layer (rather than the bottom layer) of the deposited film layer on the substrate can be exposed or hardened. This can be achieved by reducing the electron beam energy, so that most of the electrons are adsorbed on the upper layer of the film. After the top layer has been hardened, it is possible to harden all of the film layers. This can be achieved by increasing the acceleration potential of the electron beam so that the electrons completely penetrate the film layer. The feedback control circuit 400 is arranged to maintain a constant electron current that is independent of changes in the acceleration potential. The feedback control circuit 400 includes a rectifier 466. The current is sampled by a sense resistor 490 disposed between the target plate 230 and the rectifier 466. This current can also be sampled at gate 226 because some of the current is intercepted at this 20 1282125. A two-unit increase in electrical hunger 492 can buffer the signal obtained from resistor 490 and feed it back to an amplifier 496 with a target alpha resistor 494. The output of the amplifier, the potential of the gate 220, causes the increased current to cause a false bias potential drop on the gate 226 and a drop in current from the large surface area cathode 222. The resistor 494 adjusts the gain on the amplifier 496 so that any change in current due to the acceleration of the lightning is flattened by the change in the bias voltage, thereby maintaining a constant current on the target. Alternatively, the amplifier 496 #^ ώ in s ^ j out can be connected to a potential-controlled adjustable rate leakage 阙 2 9 8 to eliminate the pressure of the quarantine, the monthly increase or decrease the pressure of the free zone 238 The current produced. In addition, a wide range of current control can be provided by using feedback signals to the adjustable rate leak valve and gate 226. For further details on the beam chamber, see WilHam R (10), US Patent No. 55〇〇3?178 E Large-area Uniform Electron Source j, which has been assigned to Electron Vision c〇p〇rati〇n (currently It is also held by the assignee of this application), the contents of which are incorporated herein by reference. The process conditions for e-beam processing include the following: The process chamber pressure is between 〇-5 and 102 Torr, preferably between 1 〇-3 and 1 〇·! The distance between the substrate and the gate should be sufficient to allow ions to generate ions as they pass through the gate and substrate surface. The wafer temperature can range from 〇 to l, 〇5 (rc. electron beam energy between 〇) and 1〇〇keV. The total electronic measurement is between 1 and 丨〇〇, 〇〇〇μ(:/( : ιη2. The selected dose and energy will be proportional to the thickness of the film to be treated. The gas environment in the e_beam tool device can be the following gases: nitrogen, hydrogen, argon, helium, ammonia. , decane, gas or a combination of these gases. The e-beam current can range from 〇1 to about 100 mA. Preferably, the e-beam treatment is based on a wide, large bundle of electron beam sources from the 21 212822 area Electron is carried out, the large surface area electron beam source system can cover the surface area of the film layer to be treated. In addition, for the thick film layer, the electron beam can be divided into several low potential steps to provide the film layer from the bottom to the bottom. A uniform process of progressive hardening. Therefore, the depth of electron beam penetration during processing will vary. From 0. 5 minutes to about 120 minutes during processing. Those skilled in the art will be able to understand the time of processing with the beam. Will vary depending on one or more of the above parameters, and specific parameters are not required Excessive experimentation can be routinely obtained. In another embodiment, the operating temperature of the e-beam chamber 200 is between about -200X: to about 600 °C, such as between about 200 ° C and about 400 ° C. The electron beam energy is between about 0.5 keV and about 30 keV. The exposure dose is between about lpc/cm2 to about 4 〇 (^c/cm2, and preferably between about 5 〇pc/cm2 and about 20 (^c/cm2, for example, about 70pc/cm2. The electron beam is generally generated under pressure from 1 mTorr to ι〇〇mTorr. The gas environment of the e-beam chamber 200 may be the following gas: gas Gas, oxygen, hydrogen, argon, a mixture of gas and nitrogen, ammonia, gas or a combination of these gases. The e_beam current can range from 1 milliamperes to about 4 milliamperes, and more preferably between 5 Between milliamperes and about 20 milliamperes. The electron beam can cover an area of from about 4 square feet to about 700 square inches. The following examples show a low dielectric film layer with improved hardness. It is deposited by a slurry-enhanced chemical vapor deposition chamber. In detail, the film is manufactured by the "Producer" system produced by Applied Materials. Low dielectric constant film layer The following process gases were deposited on a 300 mm substrate at a process chamber pressure of about 5·75 Torr and a substrate temperature of about 4 ° C. 22 1282125 Octamethyltetradecaneoctane (OMCTS) ), the flow rate is about 520 seem; trimethyl decane (TMS), flow rate is about 600 seem; ethylene 'flow rate is about 2,000 seem; oxygen 'flow rate is about 1,000 seem; and atmosphere' flow rate is about 1,000 seem. Located approximately 1050 mils from the gas dispersing nozzle. Energy of approximately 800 watts at a frequency of 135 56 MHz is applied to the gas dispersion manifold for plasma augmentation/growth processing. The film layer was deposited at a rate of about 12,000 A/min and its dielectric constant (k) value was measured to be about 2.54 at 〇 1 MHz. Thereafter, the film layer is treated by an electron beam apparatus under the following conditions for about 90 shifts, for example, the e-beam chamber 2〇〇 described above. During post-treatment, the process chamber temperature is approximately 400 C, the electron beam energy is approximately 4 keV, and the current is approximately 3 milliamperes. The exposure electron beam dose is about 7〇μ(:/(:ηι2. Then argon gas is introduced into the process chamber + at about i5〇swm/guap speed for the whole hardening process. After pretreatment, the membrane layer is introduced. The electric constant is maintained at the same value, βρ 2·54. The hardness is increased from 〇66 Gpa to the shoulder, for example, as the Young's coefficient of the film increases from 4.2 GPa to 8.3 Gpa. The film thickness threshold is from About 8, the intrusion is increased to 24,00 〇A. Membrane smear, p rain - The leakage current of the membrane shield is reduced by at least i 〇, from 3.46x10 10A/cm ^ 2 to 丨 ear as low as 5.72x10 " A / square centimeter (at about 1 MW cm). The collapse potential of the film layer is increased from about 4.2 MV to 4.7 MV. Further embodiments of the present invention relate to a manufacturing-low-k dielectric constant system, the manufacturing method is here It is called 帛H. The film is made of octamethyltetracycline (OMCTS) as a precursor, dimethyl decane ((CH3)3-SiH), oxygen, 23 1282125 ethylene and helium. Diluent. According to an embodiment of the invention, the process conditions are as follows: the OMCTS flow rate is about 5000 mgm, and the triterpene base gas flow rate is about 6 〇〇 sccr», The gas flow rate is about 1 〇〇〇 seem, the ethylene flow rate is about 2000 seem, the helium flow rate is about 1000 sccm, the process chamber pressure is about 5.75 Torr, the wafer pedestal temperature is about 400 ° C, and the wafer is about 1050 mils from the process gas nozzle. And the Rf power supply is about 800 watts. After reading the specification of the present invention, a person skilled in the art can determine a more suitable deposition condition by simple experiment without undue experimentation. It must be treated as e_beam. The process conditions are as follows: The treatment dose is about 1〇〇pc/cm2, 2 minutes; the process chamber pressure (argon) is about 15亳Torr; the potential is about 4·5 keV; It is 3 milliamperes; and the wafer temperature is about 400. The thickness of the film obtained and the Young's modulus (Y〇ung, sm〇dulus) are improved. For the control of the resistive wafer, the Young's coefficient is from 14ΐ4 ( }ρ increases to about 9.563 Gpa; for a 35e_beam processed wafer, the dielectric constant remains approximately the same (the dielectric constant of the control resist wafer is about 2.52, and the dielectric constant of the wafer of the present invention is It is 2.49), but the Young's coefficient is increased from Q 699Gpa to about 4.902Gpa. About 5 阻 of the wafer is changed to 4889·3 经 by e-beam processing. These results are very important because it shows that the treatment can increase the film with poor mechanical strength without changing other characteristics. The strength of the layer. The fabrication of an integrated circuit containing a number of layers with a mechanically inferior film layer causes some problems. Taking a logic circuit as an example, the logic electrical power is made of a material having a weak mechanical strength, and the pressure is accumulated. In the upper film layer of the circuit, the upper film layer is finally broken due to pressure. In addition to the improvements described above for the e** bundle treatment formulation-II, the wetting angle (Weting an...) of the round treated by the e- 24 1282125 bundle is also reduced; The film layer is more hydrophilic. In particular, the wetting angle is reduced from the controlled retardation (4) (10) to about 40 C of the wafer treated wafer. This is very important because many photoresists are not deposited on the hydrophobic surface.

Further embodiments of the invention relate to an oxidant (eg, including but not limited to hydrogen peroxide, ozone, etc.) and a stable precursor (eg, including but not limited to trimethyl decane (TMS) or tetramethyl The decane or a precursor having a built-in metastable functional group, including but not limited to, tetradecyltetradecaneoctane (TMCTS), is used to fabricate a low-k dielectric film layer. The CVD process can be carried out at a relatively low temperature in a process chamber having the construction of Figure 2. For example, in accordance with one or more embodiments of the present invention, an operational process for a thermal deposition process such as TMS and ozone is as follows: a process chamber pressure of about 1 Torr; and a wafer holding temperature of about 400. (:; ozone flow rate is about 4000 seem; flow rate such as, for example, but not limited to, helium flow rate of about 8 〇〇〇 sccm, TMS flow rate of about 125 seem. Thereafter, the film is treated with e_beam ( Including heating the film layer simultaneously. According to one or more embodiments of the invention, a film layer is fabricated from a material comprising a metastable functional group. According to one or more such embodiments of the invention, The precursors include vinylcyclohexane (VCH), octadecyl fluorene (OMCTS), and helium as a diluent, and the film embodiment is fabricated in a process chamber having the structure of Figure 2. According to one such embodiment, the process conditions are as follows: OMCTS flow rate is about 500 mgm; VCH flow rate is about 500; helium gas flow rate is about 1 〇〇〇 seem; process chamber pressure is about 5 Torr; and one crystal 25 1282125

The crystal holder temperature is about 100 ° C; the wafer is about 800 mils away from the process gas nozzle: RF

Thermal hardening in an oven at 400 ° C for about 3 minutes. The value is about 2.77. The film is thermally cured to have an RI value of about 1 - 37' and a dielectric constant k of about 2.45. After the film layer is thermally cured, it is treated with an e-beam. The process conditions were as follows: treatment at a dose of about 200 pC/cm2 for about 2 minutes; process chamber pressure (argon) of about 15 mTorr; potential of about 4 keV; current of about 3 mA; and wafer temperature of about 400. (: The resulting film value is about 143, and its dielectric constant k value is about 2.46, while the hardness and Young's modulus are also increased. According to this means of the invention, embodiments include the use of providing metastable species (eg 'But, but not limited to, a cyclohexane or phenyl group in the film layer, a precursor, and a precursor can be provided. According to one or more such embodiments, a metastable species precursor can be provided including the following : (but not limited to) one or more of norborndiene and butadiene; and the precursors provided include the following (but not limited to): one or more of 〇MCTS, TMCTS, DMDMOS, and DEMS (stone) The oxime is bonded to ruthenium, CH3, and (〇C2H5)2 with a single bond. Further embodiments of this means according to the present invention include the use of an organic compound based on a metastable functional group, for example, VCH Or it may be built into a stone precursor, such as tert-butyl TMCTS. Further embodiments of the present invention are directed to performing multiple process steps of 26 1282125% (ie, deposition/e_beam processing) Step cycle). Finally, and choose the place to be The film is thermally hardened. According to one such embodiment, the e-beam is very short, thereby reducing shrinkage and obtaining a constant having a k value of less than 2.5. According to another embodiment of the invention, any of the foregoing implementations For example, before and/or after the selective thermal hardening step, further processing may be applied to further harden the organic ruthenium-based compound. For example, it is limited to such further processes. Treatment may include exposing it to a relatively inert plasma, such as helium or hydrogen plasma. However, in the case of the same month b electrons penetrating the membrane layer, such effects as hardening are related to changes in surface composition. The change in surface composition is caused by the fact that the organic component is sputtered off the surface, rather than the generally believed cross-linking process. However, there are some unusually thin barriers for the high carbon content. Advantages. According to one or more embodiments of the present invention, the plasma treatment can be performed in a conventional PECVD process chamber or an electrothermal regenerative apparatus. Embodiments Hypothetical Example 1 乂 The following reaction gas, process chamber pressure is about 6 Torr The substrate temperature is °C conditions. A low dielectric constant film layer is deposited on a substrate of -200 mm octadecyltetradecaneoctane (0MCTS) at a flow rate of about 52 〇sccm; ethylene, flow rate of about 2, 〇〇 〇seem ; Oxygen 'flow rate is about 1,000 seem ; and selective physique dielectric selective process but not more than half of the layer to remove the layer of such hardware 100 0 27 1282125 gas, flow rate about 1, Ο Ο 0 sccm β substrate is located about 1 〇 50 mils away from the gas dispersion nozzle. Apply about 1,200 watts, frequency i3 56MHz energy for plasma enhanced deposition process The gas used is on the dispersion manifold. After the low dielectric constant layer was deposited, it was treated in an EBK chamber at an electron beam at a dose of about 50 ° C/cm 2 at about 4 ° C. Argon gas was introduced into the process chamber at a flow rate of about 200 seem. The process chamber pressure is maintained at approximately 35 mTorr. Example 2 A low dielectric constant film layer was deposited on a 2 mm substrate using the following reaction gas, a process chamber pressure of about 14 Torr, and a substrate temperature of about 125 C. Octamethyltetradecaneoctane (OMCTS), flow rate about 210 seem; diethoxymethyl decane, flow rate about 600 seem; 1,3-butadiene, flow rate about ι, 〇〇〇seem; oxygen, flow rate approx. 600 seem ; and nitrogen 'flow rate of about 800 seem. The substrate is located approximately 1 〇5 mils from the gas dispersion nozzle. An energy of about 1,200 watts at a frequency of 13.56 MHz is applied to the gas dispersion manifold for the plasma enhanced deposition process. After the low dielectric constant layer is deposited, it is treated in an EBK chamber at an electron beam at a dose of about 400X:, about 50pc/cm2. Argon gas was introduced into the process chamber at a flow rate of about 200 seem. The process chamber pressure is maintained at approximately 35 mTorr. Fe Example 3 28 1282125 A low dielectric constant film layer was deposited on a 200 mm substrate under the following reaction gas, process chamber pressure of about 6 Torr, and substrate temperature of about 125 °C. Octahydrotetradecane octane (OMCTS), flow rate about 520 seem; propylene, flow rate about 2,0 0 seem; oxygen 'flow rate about 1, 〇〇〇sccm; and chaotic gas flow rate about 1, 〇〇〇 Sccm. The substrate is located approximately 1050 mils from the gas dispersion nozzle. An energy of about 800 watts and a frequency of 13.56 angstroms is applied to the gas dispersion manifold for the plasma enhanced deposition process. After the low dielectric constant layer is deposited, the substrate is cured at a temperature between 200 ° C and 400 ° C for about 30 minutes. A gas such as helium, hydrogen, nitrogen, or a mixture thereof is introduced into the process chamber at a rate of between 100 seem to 1 Torr and 〇〇〇 sccm to maintain the process chamber pressure between 2 Torr and 1 Torr. The RF power source is between about 200 watts and 1,000 watts and has a frequency of about 13.56 Å. A preferred substrate spacing distance is between about 300 mils and about 800 mils. Gas-Containing Example 4 A low dielectric constant film layer was deposited on a 2 mm substrate under the following conditions of a reaction gas, a process chamber pressure of about 6 Torr, and a substrate temperature of about 1 Torr. 1,3,5,7-tetramethyltetradecaneoctane (TMCTS), flow rate about 700 seem; diethoxy decyl decane, flow rate about 600 seem; 2,3-dimethyl·1,3-butyl Two women, flow rate of about 2,000 seem; oxygen, flow rate of about 1,0 0 0 sccm; and helium, flow rate of about 1,0 0 0 sccm. 29 !282125 The substrate is located approximately M50 mils from the gas dispersion nozzle. An energy of about 800 watts at a frequency of 1 3 56 MHz is applied to a gas dispersion manifold for plasma enhancement. After the low dielectric constant layer is deposited, the substrate is hardened by a temperature between (c) and 4 〇 (rc between about 3 〇 minutes. Between 100 seem to 1 〇, the rate between 〇〇〇sccm will be such as 氦A gas of gas, hydrogen, nitrogen, or a mixture thereof is introduced into the process chamber to maintain the process chamber pressure between 2 Torr and 1 Torr. The RF power source is between 7 watts to ι, 〇〇〇, The frequency is about 13.56 Å, and the preferred substrate spacing distance is between about 3 mils to about 800 mils. The hypothetical embodiment uses the following reactive gases, process chamber pressure of about 6 Torr and substrate temperature. A low dielectric constant film layer is deposited on a substrate at a temperature of about 1 〇 ° C. Vinyl decyl decane at a flow rate of about 600 seem; oxygen 'flow rate is about 80 〇 sccm; and carbon dioxide 'flow rate is about 4,800 seem The substrate is located approximately 1,050 mils from the gas dispersion nozzle. An energy of approximately 1,200 watts and a frequency of 135 56 MHz is applied to the gas dispersion for the plasma enhanced deposition process. On the tube. After the low dielectric constant layer is deposited, the electron beam is at a dose of about 50 pc/cm2 at about 400 ° C. Treatment in an EBK chamber. Argon gas was introduced into the process chamber at a flow rate of about 200 sccm. The process to pressure was maintained at about 35 mTorr. Hypothetical Example 6 30 1282125 The following reaction gas, process chamber pressure A low dielectric constant film layer was deposited on a 300 mm substrate under conditions of about 6 Torr and a substrate temperature of about 13 Ο ^ octamethyltetradecane octane (OMCTS) at a flow rate of about 483 seem ; ethylene, flow rate of about 1,6〇〇seem; carbon dioxide 'flow rate of about 4,800 sccm; oxygen 'flow rate of about 800 seem; and argon, flow rate of about 1,60 0 sccm. The substrate is located away from the gas dispersion The nozzle is approximately 1,050 mils. An energy of approximately 800 watts and a frequency of 13.56 Å is applied to the gas dispersion manifold for the plasma enhanced deposition process. After deposition, the electron beam was treated in an EBK chamber at a dose of about 400 (:, 1.5 mA, about 70 pc/cm2. The following examples show the low dielectric constant film layer of the present invention. Deposition is itself a chemical vapor deposition chamber that is part of an integrated process platform. The film was deposited by the Producer® system of Applied Materials, Inc. (Santakla, Calif.). Example 1 The following reaction gases, process chamber pressure of about 6 Torr, and substrate temperature of about 400 C were used. A low dielectric constant film layer is deposited on a substrate of 200 mm. Octamethyltetradecane octane (OMCTS), a flow rate of about 520 seem; trimethyl sulphur (TMS), a flow rate of about 200 seem; Ethylene, flow rate of about 2,0 0 sccm; oxygen, flow rate of about 1,000 seem; and 31 1282125 recorded * gas 'flow rate of about 1, 〇〇〇 sccm. The substrate is located approximately 1,050 mils (mi Is) from the gas dispersion nozzle. An energy of about 1,2 watts, frequency ι 3 · 56 μηζ is applied to the gas dispersion manifold for the plasma enhanced deposition process. The film was deposited at a rate of about 12 〇〇〇 Α / min and its dielectric constant (k) was measured at about 0.14 at 0.1 MHz. Example 2 A low dielectric constant film layer was deposited on a 200 mm substrate under the following reaction gas, process chamber pressure of about 6 Torr, and substrate temperature of about 400 °C. Octamethyltetradecane octane (OMCTS), flow rate about 520 seem; trimethyl decane (TMS), flow rate about 400 seem; ethylene 'flow rate about 2,000 seem; oxygen, flow rate about 1,000 seem; and helium The flow rate is about 1,000 seem. The substrate is located approximately 1 〇50 mils from the gas dispersion nozzle. An energy of about 1,200 watts and a frequency of 13.56 MHz is applied to a gas dispersion manifold for plasma enhancement or gas chromatography. The film was deposited at a rate of about 12,000 A/min and had a dielectric constant ("measured at about MHz1 MHz of about 2.51. Remedy 3 with the following reaction gas, process chamber pressure of about 6 Torr and A low dielectric constant film layer is deposited on a 2 mm substrate under the condition of a temperature of about 40 ° C. 32 1282125 octadecyltetradecane octane (OMCTS) at a flow rate of about 520 seem; Burning (TMS), flow rate about 60 sccm; ethylene, flow rate about 2,000 seem; oxygen, flow rate about 1,0 0 sccm; and helium, flow rate about 1,000 seem. The substrate is located in the gas dispersion nozzle Approximately 〇50 mils. Approximately 800 watts of energy at a frequency of 13.5 6 MHz is applied to a gas dispersion manifold for plasma enhanced deposition processes. The film is approximately 12,000 A/ The rate of minutes was deposited and its dielectric constant (k) was measured at about 0.17 at 0.1 MHz. Example 4 The following reaction gases were used, the process chamber pressure was about 6 Torr and the substrate temperature was about 400 °C. Conditions deposit a low dielectric constant film layer on a 200 mm substrate. Octamethyltetradecane octane (OMCTS), flow rate 520 seem ; trimethyl decane (TMS), flow rate about 800 seem; ethylene, flow rate about 2,0 0 sccm; oxygen, flow rate about 1,0 0 sccm; and helium, flow rate about 1,000 seem. The material is located approximately 1,050 mils from the gas dispersion nozzle. An energy of approximately 800 watts and a frequency of 13.56 MHz is applied to the gas dispersion manifold for the plasma enhanced deposition process. The layer is deposited at a rate of about 12,000 A/min, and its dielectric constant (k) is measured at 〇·1 MHz to be about 2.47 0 33 1282125. 复5 with the following reaction gas, process chamber pressure is about 6 Torr. A low dielectric constant film layer was deposited on a 200 mm substrate under the conditions of a substrate temperature of about 400 c. Octamethyltetradecane octane (OMCTS) at a flow rate of about 520 seem; (TMS), flow rate about 900 seem; ethylene, flow rate about 2,000 seem; oxygen, flow rate about l, 〇〇〇sccm; and helium, flow rate about 1,000 seem. The substrate is located about 1,050 mils from the gas dispersion nozzle Where is the mils. Apply about 800 watts of energy at a frequency of 13.56 MHz for the plasma enhanced deposition process. The gas was dispersed on the manifold. The film was deposited at a rate of about 12,000 A/min and its dielectric constant (k) was measured to be about 2.4 8 at 0.1 MHz. Example 6 A low dielectric constant film layer was deposited on a substrate under the following reaction gas, process chamber pressure of about 14 Torr, and substrate temperature of about 350 °C. Octamethyltetradecaneoctane (OMCTS) at a flow rate of about 210 seem; trimethyl decane (TMS) at a flow rate of about 400 seem; oxygen at a flow rate of about 600 seem; and gas at a flow rate of about 800 seem. The substrate is located approximately 45 mils from the gas dispersion nozzle. An energy of about 800 watts and a frequency of 13.56 Torr is applied to the gas dispersion manifold for the plasma enhanced deposition process. The film dielectric constant (1) was measured to be about 2.67 at 0·1 MHz. Re-shaping Example 7 A low dielectric constant film layer was deposited on a substrate under the following reaction gas, process chamber pressure of about 6 Torr, and substrate temperature of about 400 C. Octamethyltetrahydrocyclooctane (OMCTS) at a flow rate of about 520 sccm; ethylene's flow rate of about 2,000 seem; oxygen's flow rate of about 1, 〇 〇 s s c c m ; and chaotic gas flow rate of about 1, 〇〇〇 seem. The substrate is located approximately 1 〇 5 mils from the gas dispersion nozzle. An energy of about 800 watts and a frequency of 13.56 Torr is applied to the gas dispersion manifold for the plasma enhanced deposition process. The film dielectric constant (|^) was measured to be about 2.55 at 0.1 MHz. Example 8 A low dielectric constant film layer was deposited on a substrate under the following reaction gas, process chamber pressure of about 6 Torr, and substrate temperature of about 13 Torr. Octamethyltetradecaneoctane (OMCTS), flow rate about 483 sccm; ethylene, flow rate about 3,200 seem; oxygen, flow rate about 800 s c c m; and carbon dioxide, flow rate about 4,800 seem. The substrate is located approximately 1 〇 5 mils from the gas dispersion nozzle. An energy of about 1,200 watts and a frequency of 13.56 MHz was applied to a gas dispersion manifold for plasma enhancement 35 1282125. After the low dielectric constant layer is deposited, the electron beam is treated in an EBK chamber at a dose of about 4 Torr (TC, K5 milliamperes, about 225 MPa). The argon gas is introduced into the process chamber at a rate of 2 〇〇secm. The chamber pressure was maintained at 35 mTorr. Example 9 A low dielectric constant film layer was deposited on a 3 mm substrate with the following reaction gas, process chamber pressure of about 5 Torr, and substrate temperature of about 400. Octamethyltetracycline octacyclooctane (OMCTS), flow rate about 302 Sccm; dimethyl sulphur (TMS), flow rate about 600 seem; oxygen, flow rate about 1, 〇〇〇sccm; and atmosphere ' The flow rate is about 1,2 〇〇seem. The substrate is located about 35 mils (mUs) from the gas dispersion nozzle. About 800 watts, a frequency of 1 3 56 MHz, and an energy of about 25 watts and a frequency of 356 kHz are applied. The plasma enhanced deposition process. After the low dielectric constant layer is deposited, the substrate is post-treated with helium gas. The film layer is deposited at a rate of about 13, 〇〇〇A/min, and its dielectric constant ( k) is approximately between 2.97 and 3 · 〇 6. The average reflectance is i.453. The hardness of the film is about 2.2 gPa, and the uniformity is less than 2%. Approximately 13.34. The leakage current is measured at n MV/cm of approximately 4·55χ1〇. 1 amp/cm 2 and measured at 2 MV/cm is approximately 2.68χ10·9 amps/cm ^ 2 . The breakdown current is approximately 5· 93 MV/cm. The stress is about 4 〇〇χ1〇8 dynes/cm 2 and the rupture threshold is greater than 7 μm. f Example 10 36 1282125 With the following reaction gases, the process chamber pressure is about 4.5 Torr and the substrate temperature A low dielectric constant film layer was deposited on a 200 mm substrate at a temperature of about 400 ° C. Octacotetracycline octane (OMCTS) at a flow rate of about 151 seem; trimethyl decane (TMS) at a flow rate of about 300 seem ; Oxygen, flow rate is about 300 sccm; M, the flow rate is about 300 sccm; and helium, flow rate is about 600 seem. The substrate is located about 350 mils away from the gas dispersion nozzle. Approximately 400 watts, a frequency of 13.56 MHz, and an energy of about 150 watts and a frequency of 356 kHz for a plasma enhanced deposition process. After the low dielectric constant layer is deposited, the substrate is post-treated with hydrogen. 〇, 〇〇〇A/min rate is deposited, and its dielectric constant (k) is between 2.96 and 3.01. The average reflectance is 1.454. The film hardness is between 2 〇 3gPa and 2 〇 8gPa, and the average is less than 2.2%. The Young's coefficient is about 12 27. The leakage current is about 4.27x10^ amps/cm 2 measured at 2 MV/cm. The breakdown current is approximately 4.31 MV/cm. The stress is approximately 5.4 χ 1 〇 8 dynes/cm 2 and the rupture threshold is greater than 7 microns. Although Examples 9 and 1G use helium as a carrier gas, nitrogen gas can also be used as the load-carrying. It is generally believed that the use of argon as a carrier gas increases the porosity of the deposited film layer and reduces the dielectric constant of the deposited film layer. In addition, it is generally believed that the use of argon and mixed RF materials improves the film's dissociation efficiency by improving the dissociation efficiency of the precursor. Product rate. In addition, it is generally believed that the use of argon and a mixed gas source can increase the hardness and the number of Young's 37 1282125 without increasing the dielectric constant of the film. Furthermore, it is generally believed that the use of argon and a mixed RF power source reduces the chance of oblique deposition at the edge of the substrate. Further, in Examples 1-5, as the flow rate of TMS was increased from 200 seem to 600 seem, the dielectric constant value of the film was also significantly lowered. When the ratio of fatty hydrocarbon to fatty organic telluride is between 15:1 and 1:1, a low dielectric constant value is obtained. As described in Example 6, the addition of a sufficient amount of fatty hydrocarbons to the cyclic organic telluride and the fatty organic telluride provides a lower dielectric constant value that is abbreviated from the fat The value of the dielectric constant obtained in the case of a hydrocarbon is at least 7% lower. In addition, the addition of a sufficient amount of fatty organic telluride to the cyclic organic telluride and the fatty hydrocarbon can provide a lower dielectric constant value than when the fatty organic telluride is omitted. The resulting dielectric constant value is at least 3% lower, as shown in Example 7. The following examples illustrate the low dielectric constant film layers of the present invention. The film is deposited on a 2 mm substrate using a chemical vapor deposition chamber such as the pr〇ducer® system from Applied Materials, Inc. (Santa Cara, California). Example 11 The following reaction gas, process chamber pressure was about 8 Torr and the substrate temperature was about 200. (: conditions deposit a low dielectric constant film layer on a 2 mm substrate. Pinene (ATP) at a flow rate of approximately 3,000 mgm; diethoxymethyl decane (DEMS) at a flow rate of approximately 800 mgm; The carbon dioxide 'flow rate is about 1,000 seem; each substrate is located at 38 1282125 about 300 mils from the gas dispersion nozzle. 600 watts of energy at a frequency of 13.56 MHz is applied for the plasma enhanced deposition process. It is deposited at a rate of about 2,700 A/min and its dielectric constant (k) is about 5.4 measured at 0. 1 MHz at SSM 5 100 Hg CV. The hardness of each film is about 0.1 GPa. Hardening treats the first deposited layer with a heat hardening treatment. The heat hardening treatment is performed at about 425. (:, 10 Torr pressure in an inert gas for about 4 hours. A shorter heat treatment process can result in a higher k The thermosetting film layer has a low dielectric constant value of about 2.1 and a hardness of about 0.2 GPa. At 400 ° C, the E-East processing Le 7 layer is treated with a 13⁄4 warm electron beam (e-beam). The dose is 3 〇 (Wcm2, 4.5 KeV, 1.5 mA and the treatment temperature is about 400 «c. The bundle treatment lasts for about 2 minutes. After e-beam treatment The film has a dielectric constant value of about 2 · 1, which is about 6 % lower than that of the uncoated e-beam, and is close to the heat hardening. The film hardness is 0.7 GPa, compared to The e_beam processor increased by about 600%, which was about 25% higher than that of the heat-hardening treatment. At room temperature, the E-depletion second deposition layer was applied with a low-temperature electron beam ( E-beam treatment, the dose is 3 〇 (^c / cm2, 4.5 KeV, K5 mA and the treatment temperature is about 35. The beam treatment lasts for about 2 minutes. After the e-beam treatment, the dielectric of the film is often The value is about 2·3', which is about 57% lower than that without the e-beam treatment. The hardness of the film is 〇5 Gpa, which is about 4% higher than that of the untreated e-beam. Compared with the heat hardening treatment, it is increased by about 150%. 39 1282125 XM 12 A low dielectric constant film layer is deposited with the following reaction gas, process chamber pressure of about 8 Torr, and substrate temperature of about 225 °C. On a 200 mm substrate. α-Patient (ATP), flow rate approx. 3,000 mgm; diethoxymethyl decane (DEMS), flow rate approx. 800 mgm; carbon dioxide, flow rate approx. 1,500 sccm; and oxygen, flow rate approx. 1 〇〇 Sccm Each substrate is located approximately 300 mils from the gas dispersion nozzle. 600 watts of energy at a frequency of 13.56 Å is applied for the plasma enhanced deposition process. The film is approximately 1,800 people/ The rate of minutes is deposited and its dielectric constant (k) is measured at 0.1 MHz with an SSM 5100 Hg CV of approximately 1.85. The hardness of each film is about G·23 GPa. Thermal hardening The first deposited layer is subjected to a heat hardening treatment. The heat hardening treatment is carried out in an inert gas at a pressure of about 45 (TC, 10 Torr for about 30 minutes. A shorter heat treatment process can achieve a higher k value. The refractory index (RI) of the thermosetting film layer About 1.29, having a low dielectric constant value of about 2.08 and a hardness of about 0.23 GPa. 400 ° C, 200 uc / cm 2 E-beam treatment a second deposition layer is subjected to high temperature electron beam (e-beam) treatment, The dosage is 200 pc/cm2, 4.5 KeV, 1.5 mA, and the treatment temperature is about 400 ° C. The e-beam treatment lasts for about 100 seconds. After the e-beam treatment, the dielectric constant value of the film is about 2.07. It is about 27% lower than the one who does not apply e-beam treatment' and is close to the lowest value of the heat-hardening treatment. The hardness of the film layer is 〇·42 GPa' compared with the untreated beam 40 1282125. The processor increased by about 80%. tAj E-East processed the third sediment layer by applying low temperature electron beam (e-beam) treatment. The dose was 5 〇〇Hc/Cm2, 4 5 KeV, 1.5 mA and The treatment temperature is about 35 ° C. The e-beam treatment lasts for about 250 seconds. After the e-beam treatment, the dielectric constant value of the film layer is about 2·14' lower than that of the e_beam processor. About 25%. The hardness of the film layer is 0.74 GPa', which is about 220% higher than that of the un-beamed and heat-hardened processor. The following reaction gas and process chamber pressure are about 8 Torr. A low dielectric constant film layer was deposited on a 200 mm substrate at a temperature of about 225 ° C. α-Pant (ATP), flow rate of about 4,000 mgm; octamethyltetradecane octane (OMCTS), The flow rate is about 800 mgm; the milk gas, the flow rate is about 200 seem; and the carbon dioxide, the flow rate is about 2,000 seem. Each substrate is located about 300 mils from the gas dispersion nozzle. Apply 500 watts, frequency 13.56 ΜΗζ The energy is used to perform a plasma enhanced deposition process. The film layer is deposited at a rate of about 1,000 person per minute and its dielectric constant (k) is measured at SSM 5100 Hg CV of about 4 在 at 0.1 MHz. The hardness of a film is about 0.1 GPa. 40 0 ° C, 1 20 uc / cm 2 T Ε - beam treatment of the first sediment layer is applied to the southern temperature electron beam (e _ beam) treatment, the dose is 120pc / cm, 4.5 KeV, 1.5 when the amperage and treatment temperature is about 4 ° ° C. e - beam 41 1282125 treatment lasts about 30 seconds. After the e-beam treatment, the dielectric constant of the film The value is about K09, which is about 52% lower than that of the un-beamed e-beam processor. The film hardness is 〇·5 GPa', which is about 400% higher than that of the un-e-beam treatment. jL〇〇° C, 6〇〇uc/cin2 E-beam treatment of the second sediment layer is applied by high-temperature electron beam (e-beam) treatment. The dose is 6〇〇Hc/cm2, 4.5 KeV, 1.5 mA and the treatment temperature is about 400 ° c. The processing of the bundle was about 1500 seconds. After the e-beam treatment, the dielectric constant value of the film layer was about 2·2, which was about 45% lower than that of the untreated e-beam processor. The film hardness was 〇.8 GPa, which was about 700% higher than that of the untreated e-beam. Rabbit Example 14 A low dielectric constant film layer was deposited on a substrate under the following reaction gases, a process chamber pressure of about 8 Torr, and a substrate temperature of about 225 °C. --tenene (ATP), flow rate about 3,000 mgm; trimethyl decane (TMS), flow rate about 500 seem; DEMS, flow rate about 600 mgm; oxygen, flow rate about 100 seem; and carbon dioxide, flow rate about 1,500 Seem. Each substrate is located approximately 300 mils from the gas dispersion nozzle. An energy of 600 watts and a frequency of 13.56 Å is applied to carry out a plasma enhanced deposition process. The film layer was deposited at a rate of about 2,00 Å A/min and its dielectric constant (k) was measured at 〇·1 MHz with an SSM 5 100 Hg CV of about 4.3. The hardness of each film is about 〇·1 GPa. 40 0 ° C, 200 | ic / cm 2 E-beam treatment 42 1282125 deposited layer is applied by high temperature electron beam) treatment dose of 2 〇〇 Rc / cm2, 4.5 KeV, 1.5 mA and processing temperature of about 400 ° C. The e_beam processing lasts approximately 30 seconds. After the e-beam treatment, the dielectric constant value of the film layer was about 2·2, which was about 50% lower than that of the untreated e-beam processor. The film hardness was 〇·7 GPa, which was about 600% higher than that of the untreated e-beam. Example 15 A low dielectric constant film layer was deposited on a substrate under the following reaction gas, process chamber pressure of about 8 Torr, and substrate temperature of about 225 Torr. --tenkene (ATP), flow rate about 4,000 mgm; trimethyl decane (TMS), flow rate about 1, 〇〇〇seem; OMCTS, flow rate about 200 mgm; oxygen, flow rate about 1 〇〇seem; and carbon dioxide, flow rate About 1,5〇〇seem. Each substrate is located approximately 300 mils from the gas dispersion nozzle. An energy of 500 watts and a frequency of 13.56 Torr is applied to carry out a plasma enhanced deposition process. The film layer was deposited at a rate of about 1,60 Å/min and its dielectric constant (k) was measured at about 0.1 MHz at SSM 5100 Hg CV of about 4.5. Each film layer has a hardness of about 0.1 GPa. E-beam treatment at 400 ° C, 200 uc / cm 2 The deposited layer was subjected to high temperature electron beam (e-beam) treatment at a dose of 2 〇〇 gc / cm 2 , 4.5 KeV , 1.5 mA and a treatment temperature of about 400 ° C . The e-beam processing lasts for about 30 seconds. After the e-beam treatment, the film had a dielectric constant value of about 2.3, which was about 50% lower than that of the un-beamed electron beam. The film hardness was 〇·7 GPa, and 43 U82l25 was increased by about 6〇〇0/〇 compared to those without the e-beam treatment. The above examples are merely preferred embodiments of the invention. However, there are many different embodiments that can be implemented in accordance with the basic teachings of the present invention. The scope of the present invention is as follows. BRIEF DESCRIPTION OF THE DRAWINGS The features, advantages and objects of the present invention will become more apparent from the detailed description of the appended claims. The present invention is not limited to the present invention, and the drawings are merely illustrative of the typical embodiments of the present invention. For other equivalent implementations, "where: Figure 1 is based on A cross-sectional view of a CVD reaction chamber exemplified in one of the embodiments; 罘 2 is an electron beam chamber provided in accordance with an embodiment of the present invention; and FIG. 3 is provided in accordance with an embodiment of the present invention. A partial perspective view of an electron beam chamber; Fig. 4 is an electron beam chamber having one of the feedback control circuits provided in accordance with an embodiment of the present invention. [Simplified description of component symbol] 10 Process room

13 Gas Dispersion Manifold Support Column 44 12 1282125 14 Lift Motor 15 13⁄4 Vacuum Zone 17 Insulator 18 Process Gas Supply Line 19 Hybrid System 24 Jet Hole 25 RF Power Supply 32 Vacuum Pump 34 System Controller 36 Control Line 200 e- Beam chamber 220 Vacuum chamber 222 Large surface area Cathode 224 High potential insulator 226 Tree pole 228 Insulator 230 Target plate 231 Adjustable low potential power supply 232 Adjustable leak valve 238 Field white area 342 Positive ion 344 Electronic 400 Feedback control circuit 466 Rectifier 490 Inductive Resistor 492 Increases Potential Tracking 494 Variable Resistor 496 Amplifier 45

Claims (1)

1282125 Pickup, Patent Application Range: 1. A method for depositing a low dielectric constant film on a substrate, the method comprising: at least: depositing a low dielectric constant film comprising germanium, oxygen and hydrogen in a chemical vapor deposition chamber Depositing on a substrate surface; and exposing the low dielectric constant film to an electron beam condition sufficient to increase its hardness. 2. The method of claim 1, wherein the chemical vapor deposition chamber is a plasma enhanced chemical vapor deposition chamber. 3. The method of claim 1, wherein the depositing comprises: introducing a gas mixture into the plasma enhanced chemical vapor deposition chamber, the gas mixture comprising one or more compounds selected from the group consisting of An organic telluride, a fatty organic telluride, a hydrocarbon, and an oxidizing gas; and reacting the gas mixture to form the low dielectric constant film layer on the surface of the substrate. 4. The method of claim 1, wherein the condition comprises a beam current between about 1 milliampere and 15 milliamperes. 5. The method of claim 1, wherein the exposure dose of the electron beam is between about 5 Ο μ c / c m2 to about 4 Ο Ο μ c / c m 2 ° 48 I282t2S 6. The method of claim 1, further comprising the step of passing argon through the low dielectric constant film at a rate of about 15 (). 7. The method of claim 3, wherein the cyclic organic continuation compound comprises at least one hydrazine-carbon bond and the fatty organic hydrazine compound comprises at least one cleavage-chlorine bond. 8. The method of claim 3, wherein the ruthenium hydride comprises an unsaturated carbon-carbon bond. 9. A method of depositing a low dielectric constant film, the method comprising: at least: </ RTI> sufficient to deposit an uncured film layer comprising at least one cyclic group on a surface of the substrate and having a hardness of less than about 0.3 GPa Delivering a package of "one or more organic fragments and one or more gas mixtures of hydrocarbons having at least one cyclic group to a substrate surface; and electron beam sufficient to provide a dielectric constant of less than about 2.5 JL The at least one cyclic group is sufficiently removed from the uncured film layer at a hardness of 0.5 GPa. 10 κ , ' ^ A method of claim 9, wherein the one or more organic The ratio of oxygen to 石 石 石 至少 至少 至少 至少 至少 至少 。 。 。 。 。 。 49 49 49 49 49 49 49 I I I I I I I I I I I I I I I The group is a partially saturated ring having 5 to 6 broken atoms. 12. The method of claim 9, wherein the one or more ruthenium hydrides having at least one cyclic group comprise alpha-terpinene. 13. The method of claim 9, wherein the thermosetting condition comprises an electron beam having an exposure dose of between about 20 〇pc/em2 and 400 pc/cm2. 14. A method of depositing a low dielectric constant film, the method comprising: transporting, under conditions sufficient to deposit an uncured film layer comprising at least one cyclic group on a surface of the substrate and having a hardness of less than about 0.3 GPa a gas mixture comprising one or more organic fragments, one or more hydrocarbons having at least one cyclic group, and two or more oxidizing gases to a substrate surface; and an electron beam sufficient to provide a dielectric The at least one cyclic group is sufficiently removed from the uncured film layer under the condition that the electrical constant is less than about 2.2 and the hardness is higher than 〇4 Gpa. The method of claim 14, wherein the two or more oxidizing gases comprise oxygen and carbon dioxide. A method of depositing a low dielectric constant film having a dielectric constant of about 3.0 or less, the method comprising: at least: 50 16 1282125 ^ f ^ ^ allowing a gas mixture comprising: a mixture of: one or more organic tellurides; One or more fatty carbon halides having one or more unsaturated carbon-carbon bonds; and one or more oxidizing gases; wherein the low dielectric constant film is deposited on a surface of a substrate, a gas mixture onto the surface of the substrate; and after deposition of the low dielectric constant film layer, the film layer is treated with an electron beam to lower the dielectric constant of the low dielectric constant film layer. The method of claim 16, wherein the one or more organic tellurides comprise at least one fluorene-carbon bond and at least one hydrazine-hydrogen bond. 18. The method of claim 16, wherein the fatty hydrocarbon comprises two or more unsaturated carbon-carbon bonds. 1 9. The method of claim 16, wherein the condition comprises a mixed RF power supply having a frequency of 13.56 MHz and a frequency of 356 kHz. 20. The method of claim 16, wherein the gas mixture further comprises argon. 51