TW201137157A - Methods to prepare silicon-containing films - Google Patents

Abstract

Described herein are methods of forming dielectric films comprising silicon, oxide, and optionally nitrogen, carbon, hydrogen, and boron. Also disclosed herein are the methods to form dielectric films or coatings on an object to be processed, such as, for example, a semiconductor wafer.

Description

201137157 VI. INSTRUCTIONS: The benefits of the prior application of the United States Interim Patent Application No. 61/3〇1, 375, filed on 02/04/2010. FIELD OF THE INVENTION The invention relates to the preparation of a stone-containing material or film for use in various electronic applications, such as, but not limited to, stoichiometric or non-stoichiometric cerium oxide, oxynitride or oxycarbonitride. Membranes, methods and compositions. [Prior Art] A thin film of cerium oxide is often used as a dielectric in semiconductor manufacturing because of its dielectric properties. In the fabrication of germanium-based semiconductor devices, the hafnium oxide film can be used as a gate insulator, a diffusion mask, a sidewall spacer, a hard mask, an anti-reflective coating, a purification layer, and an encapsulating material, as well as other variations. The passivation of oxygen masks to other compound semiconductor devices is also becoming more and more important.

201137157 Some elements in the film may not be desired, even at lower concentrations. For example, when the dioxide film is used as a etch barrier or as a dielectric layer underneath a deep outer-line (DUV) photoresist, a small amount of nitrogen of the film may interact with the d DUV photoresist to The material properties of the photoresist are chemically amplified or poisoned and a portion of the photoresist is insoluble in the developer. As a result, the remaining photoresist may remain on the patterned edge or side J of the construction. This may be detrimental to the photolithographic patterning process of semiconductor devices. Another example of a nitrogen-free hafnium oxide film can be found in anti-reflective coating (ARC) applications. The ARC inhibits reflection of the underlying material layer during resistive imaging to provide accurate pattern replication in the energy sensitive resist layer. However, conventional ARC materials contain nitrogen such as, for example, 'nitridite and nitrite. The presence of nitrogen in the ARC layer may chemically alter the composition of the photoresist material. The chemical reaction between nitrogen and the photoresist material can be referred to as "photoresist poisoning. Materials that are poisoned by photoresist in a typical patterning step may cause inaccurate formation or patterning in the photoresist. Excessive residual photoresist afterwards, both of which can adversely affect the pR process, such as an etching process. For example, nitrogen can neutralize the acid near the photoresist and the ARC interface and cause residue formation, known as the footing ( F00ting), which further causes a curved or rounded appearance at the interface of the bottom and sidewalls of the feature rather than the desired right angle. For several applications, 'plasma enhanced chemical vapor deposition ("PEcvd") is used The yttrium oxide film is produced at a lower deposition temperature than the typical thermal chemical vapor deposition ("CVD") method. "Tetraethoxy decane (TE0S) having the molecular formula Si(〇C2H5)4 is an oxidized oxide with minimal residual carbon contamination. The pecvd of the membrane Shen 201137157 can be used as a common precursor of 'combined with one or more oxygen sources such as, but not limited to, 〇 2 or I. TEOS is used as an inert, high vapor pressure liquid, and contains more than other gases. before Objects such as SiH4 are less dangerous. > Child temperature (for example, using a cheaper base for one or more of the following reasons has a lower shift, such as less than 400. The overall driving force of 〇: cost (for example, Capability) and thermal budget (eg 'due to the accumulation of temperature-sensitive high-performance membranes.) In addition, PECVD TEOS membranes may have better gap filling and conformality at lower temperatures. However, the membrane quality of the PECVD TE〇s membrane may be : Poor 'because these membranes have no stoichiometric composition, are rich in hydrogen, have low membrane density' and / Qianlu fast (four) materials. ", need to have alternative precursors with better performance than the coffee. [Abstract] Depicting a method of forming a material or film that encapsulates oxygen and oxygen, the material or film being free of key elements such as nitrogen, carbon, dentate, and hydrogen' or, optionally, when measured by X-ray photoelectron spectroscopy (XPS), Nitrogen containing from about 〇 to about atomic weight percent and/or carbon containing from about ❹ to about 30 atomic weight per octave, and exhibiting 5% or less unevenness % can be measured using standard equations · Non-uniformity %=((maximum - scoop:; ) / Γ , , U take eight values to dare. The film deposited by this method and the precursor described in the article are not the 诒 二 TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA TA Auxiliary of the combination. Also disclosed herein is a method on a material to be processed, such as, for example, a semiconductor wafer, the dielectric film or coating is substantially free of gas and/or substantial = 201137157 carbon 'Or selectively containing lower amounts of nitrogen and carbon. In an alternative embodiment, the methods and precursors described herein provide a material having a relatively low nitrogen content, the material providing a controlled composition Nitrogen-doped oxide material. In an alternative embodiment, the methods and precursors described herein provide a material having a relatively low carbon content. The material provides a carbon-doped oxide having a controlled composition. material. In these embodiments, the material may comprise from about 〇 to about 30 atomic percent of nitrogen and/or carbon as measured by xps. In a particular embodiment, the precursor used can produce very high purity, with undetectable amounts of other elements and other Si〇2 materials that can be quantified by XPS, including carbon, nitrogen, and chlorine. And halogen. Forming a surface comprising a film comprising at least one surface of the substrate and comprising an oxygen-containing film, comprising: providing at least one surface of the substrate in the reaction chamber; and by being selected from the group consisting of chemical gases The deposition method of the phase deposition method and the atomic layer deposition method uses a ruthenium precursor comprising at least one selected from the group consisting of precursors having the following formulas 11 and m:

Η R〇-Si-H 1 Η Η RO-Si-OR1 1 Η Η RO-Si - OR2 OR1 I II III wherein R and R4R2 in the formula...! are each independently an alkyl group, a aryl group or Combining; and optionally - an oxygen source to form the film on the at least - surface, wherein the dielectric film comprises less than about $ atom% of nitrogen or carbon as measured by xps. In specific embodiments where the film comprises nitrogen or carbon, nitrogen and/or 6 201137157 carbon sources may also be introduced during the forming step. Exemplary nitrogen sources of the following materials, including but not limited to, the following materials, such as nh3, N2, NH2 (CH3), and combinations thereof, may be introduced during the forming step and/or another introduction step. The carbon and nitrogen sources can be the same. In another aspect, a method of forming a film comprising a stone and an oxygen via an atomic layer deposition (ALD) process, the method comprising the steps of: a. placing a substrate in an ALD reactor; b. comprising at least one The Shixia precursor selected from the group of precursors having the following formulas I, π and ΠΙ introduced the reactor:

Η I Η Η RO-Si-H 1 1 RO-Si-OR1 1 R0-Si-0R: 1 Η Η OR1 I II III wherein Han, 1^ and R2 in the formulae I, II and III are each independently an alkane a base, an aryl group, a thiol group or a combination thereof and any source of oxygen; c) washing the ALD reactor with a gas; d. introducing an oxygen source into the ALD reactor; e. washing the ALD reactor with a gas; And f. repeating steps b through d until a desired thickness of the dielectric film is obtained, wherein the dielectric film comprises less than about 5 atomic percent carbon and/or atmosphere as measured by XPS. In another aspect, a method of forming a film comprising ruthenium oxide on at least one surface of a substrate using an ALD or CVD method, comprising: a. placing the substrate in a reaction chamber; and b. At least one ruthenium precursor selected from the group of precursors 201137157 having the following formula: Η RO-S Η Η I Η Η RO-Si-OR1 i

H

H R〇~Si-〇R2 OR1

1 11 III wherein RH R2 of formulas I, II and m are each independently alkyl, aryl, fluorenyl or a combination thereof; and any source of oxygen is introduced into the reactor to deposit the film on the at least surface Wherein the dielectric film comprises from about 1% by weight to about 30% by weight of carbon and/or nitrogen as measured by xps. [Embodiment] The dielectric film forming a very uniform sentence is described herein (for example, when measured using the following standard equation, see 5% or less of the unevenness of the sentence %). Method of %=“maximum-minimum value//(2*average)). The dielectric film produced by the method described herein generally contains cut and oxygen. In the specific embodiment, the dielectric The eMule system does not contain any other elements such as nitrogen, carbon, gas and halogens. /5 Urgent. The wording used in rt» and 虱文 is “substantially free,” meaning that it contains 2 measured by XPS. $ n 3.腹 ▲ 』 2 atomic weight percent or less of nitrogen. In other embodiments, the ruthenium oxide film comprises other elements in an amount from about 2 Å to about 30 atom%, such as gas nitrogen and/or anti, and may be based on a spear condition or The added object used in the process has 3 other elements. In the specific embodiment, the square-r, described in the text, does not require an electric table assist and/or is tied to a low * (for example, 600 ° C or lower). The X-method described herein is carried out in an alternative embodiment τ ' using a low temperature (e.g., '450 〇c弋s from, large, i ^ or lower) thermal method. The film described herein is a dielectric constant of dielectric film 7 or 201137157 which is lower or 6 or lower or 5 or lower. Materials made in certain embodiments may also contain elements such as boron, aluminum, and/or other elements that may contribute to the preferred characteristics of the material. These can be introduced into the process as a component of a separate additive or as a substitute for the primary precursor. The method used to form the dielectric film or coating is a deposition method. Examples of suitable deposition methods for the methods disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metal organic CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition ("PECvd" High-density PECVD, photon-assisted CVD, plasma/photon assist ("ppEcvD,"), low temperature chemical vapor deposition, chemically assisted vapor deposition, hot filament chemical vapor deposition, liquid-state polymer precursors CVD, by supercritical fluid deposition, and low energy (LECVD). In a specific embodiment, the metal-containing films are deposited by plasma enhanced ald (peald) or plasma enhanced cyclic cVD (pECCVD) methods. The phrase "chemical vapor deposition method" means any method of exposing a substrate to - or more volatile precursors, the one or more volatile precursors reacting and/or decomposing on the surface of the substrate. Produce what you want to deposit. As used herein, the phrase "atomic layer deposition 3 θ self-limiting (eg, 'the amount of membrane material deposited in the respective reaction cycles remains the same" continuous surface chemistry, which can accumulate on a multi-variable substrate Conformal film or material. Although precursors, reagents, and reagents used herein may be < H ' it is understood that the precursors may be in liquid form or may be utilized by direct vaporization, foaming or sublimation or No inert body is delivered to the reaction H. In some cases the vaporized precursor 201137157 is passed through a plasma generator. In one embodiment, the ald method is used to deposit a Μ; 1 film. In another embodiment The "electric film is deposited by a CCVD method. In another embodiment, the dielectric film is deposited using a thermal cVD method. In another embodiment, the precursor can be reacted with minimal, followed by post processing While condensing on the substrate to render the material solid and assist in adhering to the deposited article, it is understood that there are many ways by which process conditions can be used to form a film from the chemical precursor. The final properties of the deposited material can be uniquely defined by the nature of the chemical precursor or additive used in conjunction with these precursors. In particular embodiments, the methods disclosed herein are avoided by the use of the introduction 6 The precursors are separated and/or during the CCVD process to avoid pre-reaction of the precursors. Thus, the dielectric film is deposited using deposition techniques such as ALD or CCVD methods. In one embodiment, The film is deposited by ALD methods by selectively exposing the surface of the substrate to the one or more ruthenium-containing precursors, oxygen source, or other precursors or reagents. #Self-restricted control of surface reactions, respective precursors Film growth is performed on the pulse length of the substance or reagent and the deposition temperature. However, once the surface of the substrate is saturated, the film growth stops. In a particular embodiment, the precursor is pure or has no other reactants. Or additives are introduced to coagulate, fill the features, or flatten the surface' followed by a reactant step to react or form a solid. Thus, the method uses an oxidation process, catalyst or other energy form (chemistry, $, radiation, f-pulp, photon or also ionized or non-radiative energy) to modify the precursor and any additives to form a solid state material. 10 201137157 In order to form a substantially nitrogen-free dielectric film containing niobium and oxygen, we do not want to contain nitrogen for the shattered precursor. What we also want is, in a specific and in vivo embodiment, the special precursor There is sufficient reactivity to deposit a film at a relatively low temperature (for example, 400 ° C or lower). Although precursor reactivity is desired, the precursor must have sufficient stability to not degrade or The change is to any significant extent (e.g., less than 1% change per year). Again, in various embodiments, we intend to perform the deposition process without plasma. Without wishing to be bound by theory, the reactivity of the substituted decane to oxidize is proportional to the number of hydrogen atoms attached to the ruthenium atom. The method disclosed herein uses a ruthenium-containing precursor, wherein the ruthenium-containing precursor is selected from the group consisting of at least one selected from the group consisting of the following formulas and precursors: 5 RO- Si-H I Η I . OR1 Η RO_S 卜 OR1 Η Η RO-Si~〇R2

1 11 III : R, R, R2 in the Chinese formula are each independently a hospital base, an aryldithiol group or a combination thereof; any other cutting precursor, any oxygen or reagent and any reducing agent form the dielectric ", electric film. The choice of precursor for deposition depends on the desired dielectric material or film. For example, the material can be directed to its chemical element content - then the case; 5 / + + "in 70" The stoichiometric ratio and/or formation of the resulting burying 1 electrosin or coating under CVD conditions is selected. The material of the alternative can also be used for multiple choices 'for example, cost, stability:, non-characteristic = his characteristic plus % at room temperature to maintain liquid abilities, volatility, points: two:: characteristics, 11 201137157 One of the methods disclosed herein is a package comprising at least one ruthenium precursor selected from the group consisting of Formulas I, II, and III: ^ Η Η R 〇-Si-H R〇-Si-〇R1 Ro'Si-〇R2 HH OR1

1 Π III wherein r and r^r2 in the formula and m are each independently an alkyl group, a aryl group or a combination thereof. In < 1 to 111 and the full text description, the phrase "alkyl" means having a linearity of 1 to 20, 岑1 5 ! 〇+, 1 25 < king π and ί to 12 or 1 to one carbon atom, Branched or cyclic functional groups. Exemplary alkyl groups include, but are not limited to, mercapto, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl, hexyl, octyl, decyl , 12-base, tetradecyl-octadecyl, isopentyl-pentyl. In style! In the description of m and the full text, the expression "aryl" means a cyclic functional group having 6 to 12 carbon atoms. Exemplary aryl groups include, but are not limited to, stupid, benzyl, tolyl, and o-diphenyl. In a particular embodiment, one or more of the alkyl, aryl and/or fluorenyl groups may be substituted or unsubstituted or have a group of atoms to which one or more atoms or hydrogen atoms are substituted. Exemplary substituents include, but are not limited to, oxygen, sulfur, dentate (eg, F, Cl, I or Br), nitrogen, boron, and phosphorus. In a specific embodiment, the ruthenium-containing precursor having the formula Z to Ιπ may have one or more substituents containing an oxygen atom. In these embodiments, the need for an oxygen source during the deposition process can be avoided. In other embodiments, the ruthenium containing precursor having formulas I through III has one or more substituents comprising oxygen atoms and also uses a source of oxygen. 12 201137157 In certain embodiments, - or more of the alkyl, aryl and/or sulfhydryl groups may be saturated or unsaturated. In particular embodiments where the one or more alkyl or aryl groups are unsaturated, they contain one or more double or triple bonds. Examples of the ruthenium-containing precursor having the formula I include: a third butoxylate, an isopropyl decane, an ethoxy decane, a n-butoxy decane, an isobutoxy sulfonate, a methoxy decane or a phenoxy Base decane. Examples of the ruthenium-containing precursor having the formula II include: di-t-butoxy decane, diisopropoxy decane, diethoxy decane, di-n-butoxy decane, diisobutoxy decane, dimethoxy Keith or dipoxyoxydecane. Examples of the ruthenium-containing precursor having the formula III include: tri-tert-butoxy decane, triisopropoxy decane, triethoxy decane, tri-n-butoxy decane, triisobutoxy decane, trioxane A decyl or triphenyloxy stone. In a specific embodiment of the method described herein, the shi-containing precursor comprises at least one of the following precursors:

Η O-Si-0

I Η Di-tert-butoxy oxane Di-p-methoxy decane Di-isopropoxy oxime In a specific embodiment, the ruthenium-containing precursor comprises ditributable tributoxide. In a particular embodiment, the methods described herein additionally comprise one or more other ruthenium-containing precursors other than the ruthenium-containing precursors of Formulas I through III above. Examples of other ruthenium-containing precursors include, but are not limited to, organic ruthenium compounds such as; oxime oxanes (eg, 'hexamethyldioxane (HMDSO) and two 13 201137157 methyl decane (DMSO)) Organic decanes (eg 'mercaptodecane; dimethyl decane; vinyl trimethyl decane; trimethyl decane; tetramethyl decane; ethyl decane; dinonyl decane; 2, 4-di Heteropentane; 1,2-dioxaethane; 2,5-dioxahexane; 2,2-didecylpropane; 1,3,5-trioxane, and these compounds a fluorinated derivative; a phenyl group-containing organic hydrazine compound (for example, dimethylphenyl decane and triphenylmethyl decane); an oxygen-containing organic hydrazine compound, for example, dimethyl dimethoxy decane ; 1,3,5,7-tetramethylcyclotetraoxane; 1,1,3,3-tetradecyldioxane; 1,3,5,7-tetradec-4-oxo-g Alkane; 2,4,6,8-tetradec-3,7-dioxo-decane; 2,2-dimethyl-2,4,6,8-tetradec-3,7-dioxo Alkane; octadecylcyclotetraoxane; [1,3,5,7,9]-quinolylcyclopentaoxane; 1,3,5,7-tetradec-2,6-dioxo- Cyclooctane; hexamethylene ring Oxane; 1,3-dimercaptodioxane; 1,3,5,7,9-pentamethylcyclopentaoxane; hexamethoxydioxane, and fluorinated derivatives of these compounds And a nitrogen-containing organic ruthenium compound (for example, hexakisodiazane; divinyltetradecyldioxane; hexakisylcyclotriazane; bis-bis-bis(N-mercaptoacetonitrile) Amine; alkaloid; dimercapto bis(N-ethylacetamide) astaxane; bis(tert-butylamino)decane (BTBAS), bis(t-butylamino)decyl decane (BTBMS) , bis(N-methylacetamide) mercapto vinyl decane; bis(N-butyl acetamide) methyl vinyl decane; hydrazine (Ν phenyl acetamide) methyl decane; Ethyl acetamide) vinyl decane; hydrazine (decyl decyl acetamide) oxalate; bis (diethylamino) phenyl decane; hydrazine (diethylamino) decane And bis(trimethyl decyl) carbodiimide. In a specific embodiment, the ruthenium containing precursor comprises a nitrogen-containing organic having at least one ruthenium-tellium moiety and at least a _Si-H moiety矽Precursor. Also 14 201137157 contains the NH Suitable precursors for breaking the Si-H moiety include, for example, bis(t-butylamino) decane (BTBAS), hydrazine (t-butylamino) decane, bis(isopropylamino) Decane, hydrazine (isopropylamino) decane, and mixtures thereof. In a particular embodiment, the precursor has the formula (R5NH)nSiR6mH4-(n + m), wherein R5 and R6 are the same or different and independently Selected from the group consisting of alkyl, vinyl, allyl, phenyl, cycloalkyl, fluoroalkyl and decyl alkyl, and wherein η is a number between 1 and 3, m is between A number from 0 to 2, and the sum of "n + m" is a number less than or equal to three. In another embodiment, the ruthenium-containing precursor comprises a decyl decane having the formula (R72N-NH)xSiR8yH4_(x+y), wherein R and R8 are the same or different and are independently selected from the group consisting of a group consisting of ethylene, propyl, phenyl, cycloalkyl, fluoroalkyl, and germylalkyl groups' and wherein x is a number between 1 and 2, and y is between 〇 and 2 The number, and the sum of "X + y" is a number less than or equal to 3. Examples of ubiquitous sulfhydryl precursors include, but are not limited to, bis(1,1-diindenyl)-decane, decyl (1,1-dimethylindenyl)decane, didimethyl Indenyl) Ethyl decane, bis(1,1-dimercaptodecyl)isopropyl decane, bis(1,indanylfluorenyl)vinyl decane, and mixtures thereof. In a particular embodiment, the precursor or additive additionally comprises a dentate decane, a borane, a borazane, a rotten acid salt, and modified versions thereof. In accordance with the deposition method, in a particular embodiment, the one or more ruthenium-containing precursors can be introduced into the reactor in a predetermined molar volume or from about 01 to about 1000 micromoles in each of the different concrete (four) The cerium precursor may be introduced into the reactor for a predetermined period of time, or about 0.001 to 15 201137157 for about 500 seconds. As mentioned above, some of the dielectric films deposited by the methods described herein may be In the presence of oxygen, an oxygen source, a reagent, or a precursor containing oxygen is formed. The source of oxygen can be introduced into the reactor in at least the form of an oxygen source and/or can be incidental to other precursors used in the deposition process. Suitable oxygen source gases may include, for example, water such as deionized water, purified water and/or distilled water, oxygen (〇2), oxygen electropolymerization, ozone (〇3), NO, N2 〇, carbon monoxide ( C〇), carbon dioxide (c〇2) and combinations thereof. In a particular embodiment, the source of oxygen is included in an oxygen source gas that is introduced into the reactor at a flow rate typically between about 2% standard cubic centimeters (s(10)). The range depends on the reaction method, the desired material, Substrate size 'deposition rate 帛, etc. The source of oxygen can be introduced prior to the precursor, simultaneously with the precursor, in a repetitive manner with the precursor in sequence or after all precursors have been introduced. In a particular embodiment, the water is present. During the deposition of the rush by the - or cyclic CVD method 'the precursor pulse may have a pulse greater than 〇: 〇 1 second of the water" and the source of oxygen may have a pulse period greater than 〇.01 seconds, while the implementation In the case of t, there may be a pulse period greater than 〇.01 seconds. During the cleaning period between pulses of another pulse, ... 1 hai, the pulse period may be as low as 0 seconds or continuous pulse without cleaning. The disclosed deposition method may be a sputum. The purge gas furnace ... ± step and one or more purge gas by-products, in the specific embodiment of the unconsumed reactants and / or reaction inertia , not (four) "(four) reaction body ° exemplary inert gas including, but not (four) ϋ, 201137157

He, Xe, 氖, η2 and mixtures thereof. In a particular embodiment, a scrub system such as Ar is supplied to the reactor at a flow rate of from about 1 Torr to about 2 〇〇〇seem for about 〇1 to 10 〇〇 seconds. The unreacted material and by-products that may remain in the reactor are washed away. In particular embodiments, for example, those embodiments in which the dielectric further contains nitrogen and/or carbon elements and/or other materials may introduce another gas such as a nitrogen source gas. The reactor. Examples of the additive may include, for example, NO, N〇2, ammonia, ammonia, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, hydrocarbons, heteroaromatic hydrocarbons, smoldering, sulphur Alkanes and combinations thereof. In a particular embodiment of the method described herein, the temperature of the reactor or deposition chamber can range from ambient temperature (eg, 25 ° C) to about 700. 0. Exemplary reactor temperature for the ALD or CVD deposition. Includes ranges with any or more of the following endpoints: 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475 , 500, 525, 550, 575, 600, 625, 650, 675 or 7 〇〇C. Examples of specific reactor temperature ranges include, but are not limited to, 2 $ it to 375 ° C, or 75 ° C to 700 ° C, or 325 ° C to 675. (In various embodiments, the pressure may range from about 1 Torr to about 1 Torr or about 1 Torr to about 5 Torr. In a particular embodiment, The dielectric film is deposited using a thermal CVD method at a pressure of between 100 mTorr and 6 MTorr. In another specific embodiment, the dielectric film is ALD by 1 Torr or more. Deposition at a low pressure range. In a particular embodiment of the method described herein, the substrate temperature in the reactor 17 201137157 or deposition chamber may range from ambient temperature (eg, 25 ° C) to about 700. An exemplary substrate temperature for the ALD or CVD deposition includes a range having any one or more of the following endpoints: 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675 and/or 700 ° C. Examples of specific substrate temperature ranges include, but are not limited to, '25C to 375 ° C ' or 75 ° C to 700 ° C, or 325. (: to 675 ° C. In a specific concrete In one example, the substrate temperature can be the same as or within the same temperature range as the reactor during deposition. In other embodiments, the substrate temperature is different from the reactor temperature during deposition. Supplying the precursors, oxygen The separate steps of the source and/or other precursors, source gases, and/or drugs can be performed by varying the time at which they are supplied to change the metered chemical composition of the resulting dielectric film. Applying energy to the precursor, oxygen source gas At least one of a reducing agent, other precursors, or a combination thereof, to initiate a reaction and form the dielectric film or coating on the substrate. This energy can be via, but not limited to, heat, plasma, pulsed plasma, Provided by heiicon piasma, high density plasma, induced power, X-ray, electron beam, photon, and remote plasma methods. In a particular embodiment, a secondary RF frequency source can be used To modify the plasma characteristics of the surface of the substrate. In a specific embodiment in which the deposition involves plasma, the method of generating electricity can include a direct electric pear production method in which direct plasma is generated in the reactor. A method of selectively generating a plasma on the outside of the reactor and supplying it to a remote plasma in the s-reactor. The ruthenium-containing precursors and/or other precursors can be delivered in a variety of ways 18 201137157 To the deposition chamber, such as a CVD or ALD reactor. In a particular embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combined liquid delivery and flash processing unit can be utilized, for example, by way of example. Turbine evaporators manufactured by MSP Ltd. of 'Snowwah, Minnesota' enable low volatility materials to be delivered in volume, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein can be delivered in pure liquid form or, alternatively, in a solvent formulation or a composition comprising the precursor. Thus, in particular embodiments, the precursor formulations can include a solvent component of a suitable end-use application that may be desirable and beneficial to form a film on the substrate. In one embodiment of the method described herein, a cyclic deposition method such as CCVD, ALD or PEALD can be utilized in which at least one ytterbium-containing precursor of the formulae I to III and combinations thereof and a source of oxygen are used, for example For example, ozone, oxygen plasma or water plasma. The gas line connecting the precipitant canister to the deposition chamber is heated to one or more temperatures as required by the program, and the vessel containing the Ishi precursors of Formulas I through III is injected to maintain one or more A temperature evaporator for direct liquid injection. Argon and/or other gases may be used as a carrier gas stream to assist in the delivery of the at least one Zeolite precursor to the reaction chamber during the pulse of the precursor. In a particular embodiment, the reaction chamber process pressure is about 1 Torr or less. In a typical ald CCVD process, a substrate such as a cerium oxide substrate is heated on a heater face of a reaction face that is initially exposed to the fused precursor to enable chemisorption of the complex. On the surface of the substrate. For example, the washing of chlorine, the 201137157 gas is washed away from the processing chamber and is not adsorbed. After washing, the source of oxygen can be... (1). After sufficient reaction, then another gas purge is performed to remove the &#; surface from the cabin. This processing cycle can be repeated to achieve the desired film thickness. In various embodiments, the steps of the method described in the text + . ^ ^ can be performed in a variety of sequences, either continuously or simultaneously (eg, at least one of the other steps = between ), and any combination thereof. The separate steps of supplying the precursors and the oxygen source gases can be varied by supplying π to the metered stoichiometric composition of the dielectric film. In another embodiment of the method disclosed herein, the dielectric films are formed using a deposition method comprising the following steps: (a) introducing a group comprising at least one precursor selected from the group consisting of:矽Precursor: Η R0-S 〇 R1 Η R〇-Si-〇R2 Η OR1 II III R, R1 and R2 are each independently a hospital base, a lanthanum RO-Si- thiol, a vat or a combination thereof; And ▲ arbitrary-oxygen source, nitrogen source or a combination thereof, and chemically adsorbing at least one month 1J of the precursor on a substrate; b. washing off the unreacted at least one stone-containing precursor by using a purge gas c. optionally introducing an oxygen source onto the heated substrate to react with at least one of the adsorbed precursors; and d. optionally washing away the unreacted source of oxygen. 20 201137157, the above steps define a cycle of one of the methods described herein; and this can be repeated until the desired thickness of the dielectric film is obtained. In various embodiments, the steps of the methods described herein can be performed in various sequences, either continuously or simultaneously (eg, during the period of the other step) and any combination thereof. . The separate steps of supplying the precursors and any oxygen source gases can be modified to provide a stoichiometric composition of the dielectric film. A multi-component dielectric film 'other precursors such as a ruthenium-containing precursor, a nitrogen-containing precursor, a reducing agent or other drug can be selectively introduced into the reactor at step "a". In this particular embodiment, the reactor temperature can range from ambient to 6 〇〇〇c. The pressure of the reactor can be maintained at iTorr or lower at various different implementations. In another embodiment of the method described herein, the dielectric film is deposited using a thermal cvd method. In this particular embodiment, the gastric method comprises: placing - or more substrates into the environment once heated a reactor having a temperature of about 7 Å <>c or a temperature of 4 Torr to 700 ° C; introducing a ruthenium precursor comprising at least one group selected from the group consisting of precursors of the following formulas I, II and III : Η RO-Si-H I Η

Η R0-S 卜 or2 OR1

III wherein R, R丨 and R2夂 a K in the formulae I, II and III are each independently an alkyl group,

Base, sulfhydryl or a combination thereof; and optionally arbitrarily a source of nitrogen, a source of nitrogen or

The source of the combination is introduced into the reactor to deposit a dielectric film on the one or more substrates, wherein the reactor is held in the process, and is maintained between 1 21 201137157 mTorr to 6 GG. Tor (four) force. In a particular implementation, the cvd reactor (iv) force can range from about G.G1T to about 1T. The reactive gas, for example, 〇2, may have a flow rate of 5 sccms. The flow rate of the ruthenium-containing precursor vapor may be between 58 and 2 〇〇seem. The deposition temperature and the reaction The wall temperature is the same. The temperature may range from ambient temperature to about 700 〇 C or from about 400 γ to about 7 〇〇〇 c. The deposition time is preset for this method to produce enthalpy of the desired thickness. The deposition rate may depend on - Or more processing parameters including, but not limited to, the deposition temperature, the flow rate, the flow rate of the carrier gas (He), the liquid mass flow of the Schlebium precursor, the temperature of the evaporator, and/or the house force of the reactor The evaporator temperature can be between 2 〇. (: to 15 〇〇 C. The deposition rate of the material can range from (10) to 1 〇〇〇 nm per (four) 。. The rate can be varied by changing the following non-limiting parameters Either to control: deposition temperature, evaporator temperature, flow rate of the lfc, flow rate of the reactive additives, and/or pressure of the CVD reactor, for example, in yet another embodiment, This method can be performed using the cyclic cvd method. In the example, the same ALD reactor can be used for the cyclic CVD method. One of the differences in the cyclic CVD method of depositing a uniform nitrogen-free film by the above ALD method is that the dose of the stellate precursor and the oxygen precursor can be greater than The dosage used for ALD, and therefore the deposition rate, can be much higher than the deposition temperature. The deposition temperature can range from about 7 〇〇〇c or 4 〇〇〇C to about 700. (In a particular embodiment, the The dielectric film or coating may be exposed to post-deposition treatments such as, but not limited to, electro-potential treatment, chemical treatment, Violet 22 201137157 external light exposure t-beam exposure and/or other treatments to affect more properties of the film. The I film has a dielectric constant of 7 or lower. Preferably, the films have a dielectric constant of about 6 or less, or about 5 or less, or about 4 or less. As mentioned previously, the methods described herein can be used to deposit a dielectric film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, ruthenium, SA, Sl3N4, organic oxidized oxide glass ( 〇SG), fluorinated oxidized olivine glass (FSG), carbonized dream , hydrogenated carbon cutting, nitrogen cutting, hydrogen sulfide cutting, carbonitriding, hydrogenation carbonitriding 7, chemical compounds, anti-reflective coatings, photoresists 'organic polymers, porous organic and inorganic materials, metals such as copper and The aluminum and diffusion barrier layers are, for example but not limited to, TiN, Ti(c)N, TaN, Ta(^N, W or WN. The films may be associated with a variety of subsequent processing steps, for example, by way of example Said, chemical mechanical planarization (CMp) and anisotropic etching procedures. The substrate can be uniform or patterned, flat or feature, planar or non-planar. Applications of deposited dielectric films include but not Limited to computer chips, optical magnetic storage, coatings on materials or substrates, micro-electromechanical systems (MEMS), nano-motor systems, thin-film transistors (TFTs), and liquid crystal displays (LCDs). The following examples illustrate the process for preparing the dielectric films described herein and are not intended to limit the invention in any way. Example 23 201137157 In the following examples, the properties of a sample film deposited on a dielectric resistivity (8 to 12 Ocm) single crystal germanium wafer substrate were obtained unless otherwise specified. CVD deposition was performed in this study using a low pressure chemical vapor deposition (LPCVD) horizontal furnace or an ATV PE0 612 furnace. The precursors are delivered to the furnace using steam draw and line temperatures adjusted according to the vapor pressure of the precursor material. The atomic layer deposition apparatus used in this study was a horizontal tube furnace designed with R&D equipped with an environmental oven for heating the delivery of precursors. The system can be from room temperature to 700. (: Deposition is performed. All plasma-based/children are processed by the Applied Materials Precisi〇n 5000 system in the 200 mm DXZ chamber equipped with the Advanced Energy 2000 radio frequency (RF) generator. Using a standard refractometer or ellipsometer measurement system, such as, for example, the FilmTek 2000SE ellipsometer, and utilizing well-known data adaptation techniques for thickness and optical properties, such as the measurement of the refractive index of such dielectric films. The characteristics of the chemical composition of these films were defined using a Multichannel Plate Detector (MCD) and an aluminum monochromatic x-ray source of Physical Electronics 5000 VersaProbe XPS spectrometer. Alka X-ray excitation (25 Ma and 15 kv) was used. Collect the xps data. Collect the low-resolution Lattice spectrum at 117 eV pass energy (called 8 energy)' 50 ms pause time and i.〇eV/step. Pass at 23.5 eV, 50 msec millisecond pause time, 〇1 The high-resolution region spectrum is collected by the eV/step. The analysis area is 45°, and the exit angle is 100 μm. The peak area is measured by the high-resolution region spectrum and the application is applied. Transmission function corrected atomic sensitivity factor determination Quantitative element scores 24 201137157 Collected and calibrated using CasaXPS nm Si02/Si. Data analysis was performed using the PHI Summitt software for data software. The axis engraving rate was approximately 12 〇A/min. The etching test was carried out in a 6:1 buffered oxide etchant ("b〇e") solution. The solution has a volume ratio of 6 parts of 40% NH4F in water and W>49% HF solution in water to form a Buffered Oxide Etchant. Place the exemplary dielectric film in HF solution for 30 seconds, then rinse and dry with deionized (DI) water before re-measuring material loss during etching. Repeat the process until such time The film is completely etched. The etch rate is then calculated from the etch time versus the slope of the etched thickness. The films are measured at three different points across the surface of the film before and after etching, along with a comparative yttrium oxide film. The thickness of the Fourier Turn was collected on the wafers using a Thermo Nicolet Nexus 470 system or similar system equipped with a DTGS KBR detector and a KBr splitter. Infrared spectroscopy (FTIR) data. The background spectrum is collected on a similar dielectric resistivity wafer to remove c〇2 and water from the spectrum. The data is often collected 32 times from 4000 to 400 cnT1 by using a resolution of 4 cm·1. Obtained in the scope. All membranes are typically corrected for baseline, normalized to a film thickness of 500 nm, and peak area and height of interest are determined. The dielectric constant of each sample film was measured in accordance with ASTM Standard D150-98. Dielectric constant, k, is utilized, for example, MDC 802B-150

The C-V curve measured by Mercury Probe is calculated. The MDC 802B-150

The Mercury Probe consists of a probe station that holds the sample and forms an electrical connection on the film to be measured, a Keithley 236 power meter, and an HP4284A LCR meter for c_v measurement. A film for c_v measurement was deposited using a germanium wafer having a relatively low resistivity (sheet current below 0.02 ohm-cm). The front contact mode is used to form an electrical contact to the film. Liquid metal (mercury) is pushed out of the surface of the wafer from the sump through a thin tube to form two conductive contacts. The joint areas are calculated based on the diameter of the tube from which the mercury is introduced. The dielectric constant is then calculated from this formula k = capacitance X contact area / film thickness. Example 1. Deposition of a ruthenium oxide film by chemical vapor deposition using di-tert-butoxy decane (DTBOS) 示 The precursor DTB0S and oxygen as a source of the oxygen were used to deposit an exemplary yttrium oxide film. The deposition conditions of each film are provided in 纟1. The characteristics of each film are provided in Table 2. Table 1 Demonstration 臈1 Deposition temperature (0C) Pressure (mTorr) Precursor flow setting (°/〇) 30 Precursor flow (seem) 14.11 Oxygen flow (seem) 20 ——— Deposition time (minutes) ^— 50 550 250 2 650 ----- 250 30 14.11 40 3 600 500 30 12.67 40 ~99^~ 4 650 500 30 13.46 40 ----- 99 5 650 250 30 14.26 40 99 6 650 250 30 10.46 40 — 30 seem = standard cubic centimeters per minute 26 201137157 Table 2

One of the exemplary films of Example 1 is shown in Figure 1 as being very homogeneous, without the purity of the film of elements such as carbon and nitrogen, typical of Χρς, TiO, and Table 3 also lists the composition of the different elements. It can be seen from the appearance of 5|| T j in Fig. 1 and Table 3 that carbon and nitrogen are detected in the films. Table 3. Chemical composition of the high-purity cerium oxide film (in atomic %) ND - amount is below the detection limit

Table 3B. Chemical composition of a nitrogen-free ceria film (in atomic %) corresponds to the spectral element concentration shown in Figure 1 64.2 34.1

27 201137157 Example 2: Thickness uniformity of the film The thickness of the nitrogen-free dioxide dioxide film formed by the method and composition described herein was measured by ellipsometry. The film deposited by the method of the present invention exhibits a sharp improvement in film uniformity in the substrate (or wafer) relative to the difference in uniformity of the nitrous oxide film deposited by the currently available method. . Figure 2 provides a comparison of the uniformity of the film thickness between the film used in the present invention and the film used in the current method, wherein the frame axis represents the measurement position of the wafer substrate and the y-axis represents the point at each point. The deviation of the thickness from the average thickness of the film. It can be seen from Figure 2 that the film deposited using the methods described herein is much more uniform across the wafer substrate than the other films. Formulas commonly used for thickness uniformity of such films, that is, uniformity = (maximum thickness - minimum thickness) / (2 * average) * ι 〇〇〇 / 0 Table 4 provides the methods described in the text. The thickness uniformity of the formed film. The results in Table 4 show that the film uniformity of the method described herein is more than 1 更好 better than the film formed using the current method (precursor). Table 4. Thickness uniformity of different ruthenium dioxide films (〇/0) ----- 1 deposition like di-butoxy decane, tert-butyl oxime, diethyl decane film uniformity 1.43 35.0 18.74 Example 3: K and Dielectric Constant 28 The dielectric constant of the yttrium oxide film formed by the method described in Xiao Wenzhong is derived from the c_v plot shown in FIG. The dielectric constant of the film was found to be 4.47 for the conventional thickness of the film and the contact area of the probe used. Comparative Example 4 of a film deposited by a precursor of a second butoxyoxane precursor: the plasma-enhanced cvd utilization and ethoxy decane in different process conditions in the following examples, unless otherwise specified, the properties are Deposition = Dielectric Resistivity (8-12 (4) Single crystals were obtained from the sample film on the wafer substrate. The deposition temperatures were 200, 300, and 400. (: Table 5 is provided for comparing the precursors or the second third. A combination of oxydecane (DTBOS) and comparative precursor tetraethoxyl (TE〇_3 different processing conditions. These three different processing conditions are labeled as BL·b bl_2 and BL-3. Table 5 Process Conditions BL-1 --'^ BL-2 BL-3 month 'J drive flow (seem) 107 45 27 He (carrier) ------- 1000 1000 1000 02 1100 ------ 1100 -- ---. 700 Pressure (Torr) 8.2 "---- 8.2 3.5 Interval (Mil) 500 500 ' ^--^ 800 Power Density (W/cm2) 2.27 - A 2.27 0.87 *---- – Table 6 provides a comparison of the κ value, deposition rate and wet etch rate for TEOS versus DTBOS for this B L1 condition 29 201137157. DTB for the volume flow of the same precursor The deposition rate of OS is higher than that of TEOS. This shows that DTBOS may be more efficient than TEOS in terms of PECVD deposition. Furthermore, the WER of the DTBOS deposited film is equal to or better than the WER of the TEOS deposited film. This implies the use of the DTBOS. The equivalent or preferred density of the SiO 2 film deposited by the precursor. Table 6 K value D/R (A/min) WER A/min, 6:1 BOE T TEOS DTBOS TEOS DTBOS TEOS DTBOS 200 4.99 5.78 5310 6174 4278 4096 300 4.43 4.55 4644 5200 2958 2844 400 4.21 4.16 3072 3714 2100 1888 Table 7 provides a comparison of the K value, deposition rate and wet etch rate for TEOS versus DTBOS using the BL2 processing conditions. For the volume flow of the same precursor, DTBOS The deposition rate is higher than TEOS. This demonstrates the higher efficiency of the DTBOS precursor for PECVD deposition. However, the WER is equal or better than the WER of the TEOS film. This implies the equivalent of the SiO2 film formed by DTBOS. Or better density. 30 201137157 Table 7 K value D/R (A/min) WER A/min, 6:1 BOE T TEOS DTBOS TEOS DTBOS TEOS DTBOS D/RD/R 200 4.65 4.89 1201 1722 2958 2602 300 4.39 4.52 1003 1430 2304 1980 400 4.19 4.46 1045 1004 1840 1726 Table 8 provides a comparison of the K value, deposition rate, and wet etch rate for TEOS versus DTBOS for the BL3 processing conditions. The deposition rate of DTBOS is equal to TEOS for the volumetric flow rate of the same precursor. However, the WER is clearly better than the WER of the TEOS film. This implies a better density of the SiO 2 film formed by DTBOS. In addition, DTBOS has a lower K value, suggesting less moisture absorption. Table 8 K value D/R (A/min) WER A/min, 6:1 BOE T TEOS DTBOS TEOS DTBOS TEOS DTBOS 200 5.9 5.4 1014 1003 5382 4075 300 4.45 4.38 818 803 3504 3006 400 4.25 4.13 655 416 2340 2007 31 201137157 Figure 4 shows a comparison of the WER of the deposited films using all of the baseline conditions and deposition temperatures (e.g., BL-1, BL-2 and BL-3 and 200, 300 and 400 °C) described in Table 3. The DTBOS film has a lower WER for the same K, suggesting a higher density and higher quality oxide film. Therefore, DTBOS can produce a film superior in quality to TEOS at a relatively low temperature of PECVD deposition. Table 9 below provides the breakdown voltage (Vbd) of TEOS and DTBOS at different temperatures under process conditions BL1, BL2 and BL3 as defined in Table 5 above. Typically, the penetration voltage is 8 to 12 MV/cm and the two precursors are comparable. Figures 5, 6 and 7 show the comparison of the leakage current versus the electric field for the TEOS deposited film compared to the DTBOS deposited film deposited at 200 ° C and 300 ° C. Figure 5 provides a plot of leakage current vs. electric field for TE1 versus DTBOS at 200 °C and 300 °C for BL1 conditions. Since DTBOS has a higher K and WER at 200 °C than TEOS in terms of BL1, the impact on film leakage is also seen. However, this is the only condition that DTBOS shows worse leakage performance than TEOS. Referring to the 300 °C data and as seen in Figures 6 and 7, the DTBOS Si02 leakage is generally superior to the TEOS Si02 leakage. Figure 6 provides a plot of the leakage current vs. electric field for TEOS versus DTBOS at 200 °C and 300 °C for BL2 conditions. Even though DTBOS has a higher D/R; the leakage of the DTBOS SiO2 film is lower than that of the TEOS SiO2 film, confirming excellent electrical properties and supporting the WER data. 32 201137157 Figure 7 provides a plot of the leakage current vs. electric field for TEOS versus DTBOS at 200 °C and 300 °C for BL3 conditions. In general, in the case of BL3, the leakage of DTBOS is lower than that of TEOS. Table 9 BL1 TEOS DTBOS 200°C 9.6 12.7 (with leakage) 300°C 9.68 10.26 400°C 7.9 9.26 BL2 TEOS DTBOS 200°C 10.4 10.29 300°C 10.7 8.67 400°C 9.5 9.7 BL3 TEOS DTBOS 200°C 10.9 9.89 (Leakage) 300°C 9.7 (with leakage) 9.74 400°C 9 9.61 Figure 8 provides data on dynamic secondary ion mass spectrometry of DTBOS compared to bis(t-butyl)amino decane (also known as BTBAS). -SIMS). As is known from the BTBAS XPS data, these CVD processes typically provide about 10 atomic percent carbon (except hydrogen). In this way, compared with Table 3, the amount of carbon in the DTBOS film was not detected. The D-SIMS data indicates a carbon content of approximately two orders of magnitude lower, indicating the actual amount of carbon in these membranes, as compared to the BTBAS XPS data, 33 201137157, possibly < o.i atomic %. ALD deposition data from DTBOS is provided in Table 10. The deposition of cerium oxide is evidenced by the proper refractive index of these films. Table 10 Wafer temperature source pulse (seconds) Ozone pulse (seconds) Cycle number average thickness (A) Average refractive index angstrom / cycle uniformity (%) 400 0.5 2.0 500 41 1.3379 0.0813 20.90 600 0.5 2.0 500 75 1.5547 0.1503 15.30 600 0.5 2.0 500 80 1.5425 0.1607 18.67 650 0.5 2.0 500 239 1.4365 0.4783 34.29 300 1.0 2.0 500 27 1.4457 0.0543 25.77 400 1.0 2.0 500 48 1.2477 0.0967 10.34 500 1.0 2.0 500 50 1.4343 0.1000 9.00 600 1.0 2.0 500 114 1.5324 0.2287 19.24 650 1.0 2.0 500 335 1.4574 0.6690 32.29 600 2.0 2.0 500 282 1.3983 0.5647 32.05 650 2.0 2.0 500 559 1.4476 1.1180 32.56 The invention also includes a package having a reactant as described above, comprising an electropolished stainless steel container having an inlet and an outlet, The inlet and outlet 34 201137157 have high purity and low dead space valves. . The human has a third butoxy decane, isopropyl decane, ethoxy decane, n-butoxide, oxetane, isobutoxy decane, methoxy decane, pentoxy decane, and a second butoxy decane. , diisopropoxy decane, diethoxy decane, di-n-butoxy oxazepine, diisobutoxy decane 'dimethoxy decane, dipentoxy ketone, tri-tert-butoxy decane, Triisopropoxy decane, triethoxy zephyr, di-n-butoxy decane, triisobutoxy decane, trimethoxy decane or tridecane. The reactants and methods of the present invention can be used to fabricate devices selected from the group consisting of: optical devices, magnetic data storage devices, coatings on a building material or substrate, microelectromechanical systems (MEMS), Nano T$ system, thin film transistor (TFT) and liquid crystal display (LCD) » [Simplified illustration] Figure 1 provides the results of the 臈-ray photoelectron spectroscopy (XPS) deposited using the method described in Example 1. . Figure 2 provides the thickness uniformity of three exemplary crucibles deposited using the third butyl sinter, diethyl decane, and di-t-butoxy decane (DTBOS) according to the method described in Example 2. Figure 3 provides a graph of the deposition of the dielectric constant obtained from the exemplary film using one of the process conditions provided in Table 1 using the precursor DTBOS. Figure 4 shows the use of the BL1 conditions described in these examples for three different deposition temperatures or 400. (:, 300oC, 200. (: Comparison of the wet residual rate (WER) of the deposited germanium. 35 201137157 Figure 4 shows that the DTBOS deposited film has a lower WER than the TEOS film at all temperatures. Figure 5 provides a comparison of TEOS The leakage currents at 200 ° C and 300 ° C versus the electric field are plotted against the BL1 conditions described in Table 3 of Example 4 for DTBOS. Figure 6 provides TEOS vs. DTBOS for Table 3 of Example 4. The leakage currents plotted at 200 ° C and 300 ° C versus the electric field are plotted in the BL2 conditions described. Figure 7 provides TEOS versus DTBOS for the BL3 conditions described in Table 3 of Example 4. The leakage currents at 200 ° C and 300 ° C are plotted against the electric field. Figure 8 provides a comparison of DTBOS in a CVD film deposited from those precursors with bis(t-butyl)amino decane (BTBAS). Dynamic secondary ion mass spectrometer data (D-SIMS). 36

Claims (1)

201137157 VII. Patent application scope: 】 A method for forming a dielectric film on at least one surface of a substrate, the method comprising: providing at least one surface of the substrate in a reaction chamber, and introducing a precursor of a ruthenium The reaction chamber forms a dielectric film comprising at least one group selected from the group consisting of precursors of the following formulas I, II and III: ^ Η Η R0_^i_H RO-Si-OR1 RO-Si-〇R2 HH 0Ri 11 III wherein the group, the merging group or a combination thereof in the formulae I, II and III. R1 and R2 are each independently alkyl, and aryl is selected from the group consisting of oxygen. 2. The method of claim 帛i... the source of at least the source, the nitrogen source or a combination thereof! Into the $ reaction cabin. The method is at least deposited or as described in the patent application, wherein the formation is selected from the group consisting of cyclic chemical vapor deposition, plasma enhanced chemical vapor deposition. 4, such as the third patent range of the application of patents. The method of claim 1, wherein the 1月1j drive comprises two of the 矽 precursors comprising two. 5. The method of claim 1 is the third pentoxy oxime. 37 201137157 6. The method of claim 2, wherein the source of oxygen comprises oxygen. 7. The method of claim 2, wherein the source of oxygen comprises ozone. • a method of forming a dielectric film comprising germanium and oxygen by atomic layer deposition. The method comprises the steps of: a. placing the substrate in an ALD reactor; b. comprising at least one selected from the group consisting of The 矽 precursor of the group of precursors of π, π and ιπ is introduced into the ALD reactor: Η Η Η RO-Si-H RO-Si-OR1 RO-Si-OR2 Η H OR1 1 π in where I R, R1 and r2 in II and III are each independently an alkyl group, an aryl group, a brewing group or a combination thereof; C. washing the ALD reactor with a gas; d· introducing an oxygen source into the ALD reactor; Washing the ALD reactor with a gas; and f. repeating steps b through d until a desired thickness of the dielectric film is obtained, wherein the dielectric film comprises up to about 30 atomic percent nitrogen as measured by XPS. 9. The method of claim 1, wherein the source of nitrogen is introduced into the reaction chamber. 38 201137157 ίο. The method of claim i, which utilizes the thermal cvd method, which causes the dielectric film to contain up to about 9% by weight of gas as measured by XPS. 11. The method of claim 1 , wherein at least a source selected from the group consisting of an oxygen source, a nitrogen source, or a combination thereof is tucked into the reaction chamber. 12. A film produced by the method of claim 3, which has the same and which forms Sia〇bNccdHeBf 'where a is 1〇 to 5〇 atom%, and b is 1〇70 atoms/〇' c is 〇 to 3 〇 atomic %, 廿 is. To atomic %, e is 0 to 50 atom%' and [is 〇 to 3〇 atom%. 13. An electropolished stainless steel container having an inlet and an outlet having high purity low dead space vaives, the trough 3 having a second butoxy decane, isopropyl decane, Ethoxy decane, n-butoxydecane 'isobutoxy decane, decyl decane, pentoxy decane, a first butoxy decane, diisopropoxy decane diethoxy decane, di-n-butyl Oxygen stone simmering, diisobutyoxy shixiyuan, dimethoxy zexi sulphide, bismuth oxide yoshiyuan, tris-butoxy sulphide, triisopropoxy zexiyuan, triethoxy oxane N-butoxy decane, diisobutoxy decane, trimethoxy decane or triphenyloxy; 14. One type of patent pending in use! The device manufactured by the method of the present invention is selected from the group consisting of: an optical device, a coating of a magnetic data storage device on a branch material or a substrate, a micro-motor system 39 201137157 (MEMS), nano Motor systems, thin film transistors (TFTs) and liquid crystal displays (LCDs).