TW201204860A - Metal film deposition - Google Patents

Abstract

Disclosed are modified Atomic Layer Deposition processes used to deposit metal films on a substrate.

Description

201204860 VI. INSTRUCTIONS: Cross-application for related applications This application claims to be filed on July 22, 2010 by U.S. U.S. Provisional Application No. 61/366,810 and March 3, 2011 The benefit of the present application is hereby incorporated by reference. [Prior Art] Atomic Layer Deposition (ALD) is a process for depositing a thin film on a substrate. The typical film thickness can vary from a few angstroms to hundreds of microns depending on the particular deposition process. In a standard ALD process, the gas phase of the precursor is introduced into a reactor where it is contacted with a suitable substrate. Excess precursor can then be removed from the reactor by flushing with an inert gas and/or pumping the reactor. A reactant (e.g., hydrazine 3 or NH3) is introduced into the reactor where it reacts with the absorbed precursor in a self-limiting manner. II remove any excess reactant from the reactor by flushing and/or evacuating the reactor with an inert gas. If the desired film is a metal crucible, the two-step process can provide the desired film thickness or can be repeated until a film having the desired thickness is obtained. ^ Or if it is a bimetallic film, the vapor of the second metal-containing precursor can be introduced into the reactor after the above two steps. The second metal-containing precursor will be selected based on the nature of the deposited bimetallic film f. After introduction into the reactor, the second metal-containing precursor is in contact with the substrate. Any excess second metal-containing precursor is removed from the reactor by flushing and/or evacuating the 201204860 reactor. Once again, the reactants can be introduced into the reactor to react with the second metal-containing precursor. Excess reactants are removed from the reactor by flushing and/or evacuating the reactor. If the desired film thickness has been obtained, the electricity can be terminated. However, if a thicker film is required, the entire four-step process can be repeated. A film having a desired composition and thickness can be deposited by alternately providing a metal-containing precursor, a second metal-containing precursor, and a reactant. Unfortunately, to date, standard ALD processes have not been successful in depositing all of the relevant films in a semiconductor 'photovoltaic, LCD_TFT or flat panel process. O.Meara #人(Electrochemical Society 21st 欠2 meeting (7), ^(10)(4) Society 210th Meeting), Abstract 1〇64) proposes a molecular layer deposition process for improving sm deposition. The use of dioxane (DCS)e in a standard CVD process, SiN deposition using DCS+NH3 does not occur at temperatures below 6 〇 (rc. Using an alternative method derived from atomic layer deposition (ALD), 〇, Meara It has been demonstrated that the use of DCS and ammonia to grow a thin SiN layer at about 500 ° C is feasible. In this alternative method, DCS is introduced separately at high flow rates and relatively high pressures (about 6 Torr / 800 Pa). The system is then rinsed, followed by NH3 alone (also about 6 Torr/800 Pa). Long lead times are used to make the surface dry. The film thickness is shown to increase linearly with the number of cycles. However, the time required for each cycle is approximately or For 24 minutes, it is not cost competitive from a manufacturing point of view. Testing for higher temperatures results in DCS decomposition and uneven film growth.

Nakajima et al. (Applied Physics Letters 79 (2001) 665) describe a conceptually similar approach. Nakajima et al. switched to 375. (: and 201204860 200 Torr (26,664 Pa) SiCl4 pulse, then rinse the chamber, then introduce ΝΑ ' but the substrate temperature is about 55 (TC and the pressure is 5 〇 0 Torr (66, 661

Pa). A full cycle takes about 1 minute. This process forms an insulating tantalum nitride layer and requires the use of a co-reactant.

The ALD cycle of Table 2, which contains 300, is disclosed in U.S. Patent Application Serial No. 2/6,681, the entire disclosure of which is incorporated herein. (: Hfcl2 pulse is applied, the temperature is raised to 420 C for 2 minutes and then the cooling temperature is 4 minutes. Even if the to reactant is not directly introduced (paragraph 0123), the obtained film is still Hf〇2. It is assumed that the oxygen source is from the transfer mode. The moisture of the residue in the group (paragraph 122) However, the obtained film still has a high C1 content (paragraph 123). There is still a need to deposit deposition during the fabrication of semiconductor, photovoltaic, LCD-TFT or flat panel. ALD Process for Metal Films. SUMMARY OF THE INVENTION A method for depositing a metal film on one or more substrates is disclosed. The disclosure includes a temperature in a reactor containing at least one substrate, which will contain a pulse of a metal body. Introducing into the reactor such that the surface of the at least one substrate (4) is saturated with the metal precursor and the at least part is removed only by increasing the temperature of the reactor to a temperature at which the decomposition temperature of the metal-containing precursor is ^ = a portion of the precursor to form a metal layer. The resulting metal layer is in the range of from about 70 atomic percent to about (10) atomic percent, preferably from about 9', sub-percent to about 1 atomic percent. Uncover The method comprises introducing a metal-containing precursor pulse into a reactor of 4::: at least one substrate, wherein the temperature of the reactor is lower than a decomposition temperature of the substrate, so that the surface of the at least one substrate passes at least 201204860 The partially metal-containing precursor is saturated, and the metal layer is formed on the at least one substrate only by raising the temperature of the reactor to a temperature higher than the decomposition temperature of the metal-containing precursor. In another alternative, the disclosed method is basically Composed of the following steps: setting the temperature in the reactor containing at least one substrate, pulsing the metal-containing precursor into the reaction n +, causing the surface of the at least one substrate to pass to > the partial metal precursor to be saturated, in the rinsing Removing at least a portion of the at least a portion of the metal-containing precursor during the cycle by removing the temperature of the reactor above the decomposition temperature of the metal-containing precursor to form a metal layer and repeating the steps until a metal having a desired thickness is obtained In another alternative, the disclosed method consists essentially of the following steps: • introducing a metal-containing precursor pulse into which is placed at least In the reactor of the substrate, the temperature of the reactor is lower than the decomposition temperature of the metal-containing precursor, so that the surface of the at least one substrate is saturated with at least a portion of the metal-containing precursor, and the temperature of the reactor is raised during the flushing cycle. Forming a metal layer on the at least one substrate to a temperature higher than a decomposition temperature of the metal-containing precursor, and repeating the steps until a bismuth film having a desired thickness is obtained. The disclosed methods each include one or more of the following states Example: • Repeat the method step; • The metal concentration in the metal layer is in the range of about 70 atomic percent to about 1 atomic percent, preferably about 90 atomic percent to about 1 atomic percent; • the lower temperature is about 20 From °C to about 40 (TC, preferably from about 50 ° C to about 300 ° C; 201204860 • Higher temperatures from about 100 ° C to about 600. • Within the range of 〇; • Lowering the temperature from a higher temperature to a lower temperature by gas cooling on the back side or by high-speed flow gas cooling; • The metal-containing precursor is selected from the group consisting of Α1Η3· tertiary amine, A1H3. cyclic amine, A1H2 (BH4) And A1H2 (BH4): a group of tertiary amines; • a metal-containing precursor selected from the group consisting of A1H3. NMe2Et, A1H3. Mercaptopyridine and AlH2(BH4): NMe3; • Metal-containing precursors The oxidation state of the metal is ruthenium; • The metal-containing precursor is selected from the group consisting of: (tricarbonyl) (benzene) crane [W (Bz) (CO) 3], (trisyl) (benzene) key [M〇 (Bz)(c〇)3], (toluene) (cyclohexadiene) ruthenium, (cyclohexane) (tricarbonyl) ruthenium [Ru(Chd)(CO)3], Ru3(CO)丨2 (nonylcyclohexadiene) (tricarbonyl) ruthenium [Ru(Me-CHD)(CO)3] and bis(1,3,5-trimethylbenzene) ruthenium and bis(13 5_trimethylbenzene) ruthenium; a noble metal; and the metal-containing precursor is selected from the group consisting of (A stupid X-cyclohexadiene) ruthenium, (cyclohexadiene) (tricarbonyl) ruthenium [Ru(Chd)(c〇) 3], (nonylcyclohexadiene) (tricarbonyl) hydrazine [Ru(Me-CHD)(C〇)3] and rU3(c〇)Notation and Nomenclature 12 Certain terms are used in the following description and claims to refer to particular system components. This standard uses the standard abbreviations from the elements of the periodic table. It should be understood that elements may be referred to by such abbreviations (e.g., Ru refers to 钌, Ta refers to 'group, Nb refers to 铌, etc.). 201204860 The term 'independently' as used herein, when used to describe an R group, is understood to mean that the R group referred to is not only independent of other R groups having the same or different undercut or superscript. Select 'and also independently select with respect to any other species of the same R group. For example, in the formula MR^NR^R^G-x), wherein 乂 is 2 or 3' two or three R 丨 groups may, but need not be identical to, or identical to, or identical to R3. Further, it should be understood that the meaning of the R groups when used in the different formulas are independent of each other unless otherwise specified. The term "alkyl" as used herein refers to a saturated functional group containing only carbon and a hydrogen atom. Further, the term "alkyl" means a straight chain, a branched chain or a cyclic alkyl group. Examples of direct bond groups include, but are not limited to, fluorenyl, ethyl 'propyl, butyl, and the like. Examples of branched alkyl groups include, but are not limited to, a third butyl group. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl and the like. As used herein, the abbreviation "Me" means methyl; the abbreviation r Et" means ethyl; the abbreviation "Pr" means propyl; the abbreviation "iPr" means isopropyl; the abbreviation "Bu" means butyl (n-butyl) The abbreviation "tBu" means the third butyl group; the abbreviation "sBu" means the second butyl group; the abbreviation "Cp" means the cyclopentadienyl group; the abbreviation "the oxime ring has an alkenyl group, the abbreviation "Bz" means benzene; the abbreviation " C0(j) means cyclooctyl dibasic; the abbreviation "acac" means acetylpyruvate; the abbreviation r R_NacNac" means N-alkyldiketiminate; the abbreviation "R_acNac" means N-alkyl N-alkyl ket〇mininate, also known as enaminoketonate; the abbreviation "hfac" refers to hexafluoroacetoxypyruvate; the abbreviation "tmhd" refers to 2,2,6,6- Tetramethyl-3,5-heptanedione; abbreviation

S 8 201204860 〇d”曰2,4_辛二嗣基;, the abbreviation “dmamp” means 1-dimethylamino 2·methyl-2-propanol vinegar; the abbreviation “_Μ” means 2 , 6-dimethyl-3,5 heptanedione, and the abbreviation "ΜΑΒΟ" refers to κ-didecylamino-2-methyl-2-butoxy. In order to further understand the nature and objects of the present invention, reference should be made to the following detailed description. [Embodiment] An improved atomic layer deposition (ALD) method for depositing a metal film on a substrate is disclosed. The disclosed method can be applied to the fabrication of semiconductor, photovoltaic, LCD_TFT or flat panel devices. Improved ALD reactors suitable for practicing the disclosed methods are also disclosed. The method disclosed includes setting a temperature in a reactor containing at least one substrate, introducing a metal-containing precursor pulse into the reactor, saturating a surface of the at least one substrate with at least a portion of the metal-containing precursor, and merely by causing the reactor The temperature is raised to a temperature above the decomposition temperature of the metal-containing precursor to remove at least a portion of the ruthenium-containing precursor to form the metal $. The metal concentration in the resulting metal layer ranges from about 7 atomic percent to about 1 atomic percent, preferably from about 90 atomic percent to about 100 atomic percent. Alternatively, the method disclosed includes introducing a metal-containing precursor pulse. In the reactor in which at least one substrate is disposed, the temperature of the reactor is lower than the decomposition temperature to the sub-driver, so that the surface of the at least one substrate is saturated with at least the metal of the boring tool, and only by the A temperature of the reactor is raised to a temperature higher than a decomposition temperature of the metal-containing precursor to form a metal layer on the at least one substrate. The term "only" means that the steps are not performed using other steps. In other words, in 201204860, only the temperature is raised to remove a portion of the at least partially metal-containing precursor or only raise the temperature to form a metal layer. No reactants are required in the step. In another alternative, the disclosed method consists essentially of setting a temperature in a reactor containing at least one substrate, introducing a metal-containing precursor pulse into the reactor, and passing the surface of the at least one substrate to J Part of the metal-containing precursor is saturated, and a portion of the at least a portion of the metal-containing precursor is removed to form a metal layer by repeating the temperature of the reactor to a temperature at which the decomposition temperature of the metal-containing precursor is raised during the rinse cycle, and repeating These steps are until a metal film having a desired thickness is obtained. In another alternative, the disclosed method consists essentially of the following steps: introducing a metal-containing precursor pulse into a reactor in which at least one substrate is placed; the temperature of the S-thin reactor is lower than the decomposition temperature of the metal-containing precursor Forming a surface of the at least one substrate with at least a portion of the metal-containing precursor, forming a metal layer on the at least one substrate during a rinse cycle by raising the temperature of the reactor to a temperature above a decomposition temperature of the metal-containing precursor And repeating the steps until a metal film having a desired thickness is obtained. The phrase "consisting essentially of" limits the disclosed method to the specified steps, plus any steps that do not materially affect the basic and novel characteristics of the disclosed method. More specifically, in the alternative The method claimed by the applicant is to produce a metal ruthenium without using a reactant. However, if other processing is performed, such as adding another metal to the metal film to produce a bimetal film, the reactants may be used to deposit other metals as needed. In a second alternative, the scope of the method is limited to the production of a metal film without the addition of another metal. 0 10 201204860 Suitable metal-containing precursors include a metal containing from the 帛3 rows to the 12th 周期 of the periodic table (a Ga, In, T1, Ge, Sri Bars: Ge Sn, Pb, Sb, and Bi): Organometallic precursors. The metal-containing precursor preferably contains a noble metal (i.e., M, Rh, Pd, Ag, Re, 0s, Ir, Pt, Ai^Hg). In an alternative, the oxidation state of the metal containing the metal precursor is ruthenium. Compared with the metal with a more south oxidation state, it is easier to remove the ligand from the metal oxide state, because the metal and the ligand are both dissociated into; the substance. Applicant Xianxin Metal The dissociation of compounds in which the oxidation state is ruthenium does not require the use of reactants (the > h2) but only requires heating. Applicants have a higher oxidation state of the metal - some compounds may require the use of a reducing agent to form a metal film. Depending on the metal and the ligand, the disclosed method can be applied to some oxidation states above 0. 4. Exemplary metal-containing precursors (wherein the oxidation state of the metal is 0) include, but are not limited to, (nonyl) (cyclohexadiene) ruthenium, Ru3(c,o)12, (cyclohexadiene) (trisyl) fluorene, (trisyl) (phenyl) crane [w(Bz)(co)3], ( Tricarbonyl)(phenyl)molybdenum [Mo(BZ)(co)3], bis(13 5/nonphenyl)anthracene and bis(1,3,5-triphenylene) button "Ru compound cyclohexadienyl" Independently substituted by one or more C! to C6 alkyl groups, such as Ru(Me_cyclohexene) (CO) 3. These exemplary metal-containing precursors are commercially available. The metal-containing precursor should have Suitable for Explain the appropriate decomposition degree of the method. Those skilled in the art will recognize that molecular decomposition does not occur at a certain temperature and occurs within a certain temperature range. The claimed decomposition, θ is the highest allowable self-saturated surface saturation. Temperatures. Exemplary metal-containing precursors suitable for use in the disclosed methods and their decomposition temperatures are provided in Table i below. 11 201204860

Precursor decomposition temperature A1 A1H3 tertiary amine ~120 °C A1H3 cyclic amine ~120 °C A1H2 (BH4) and A1H2 (BH4): tertiary amine ~120 ° C trimethyl aluminum > 350 〇 C A1H3 · methyl Pyrrolidine ~130 ° C Aluminum hydride: R3N: A1H3, where R is alkyl ~ 120 ° C NMe3: AlH3 (TMAA) ~ 120 ° C Me2EtN: AlH3 (DMEAA) ~ 120 ° C A1H2 (BH4) XN (CH3) 3 (TMAAB) ~120°C Nb NbCl5 320〇C bis(1,3,5-trimethylbenzene)铌200°C Zn Diethylzinc~300°C or above 300°C Co Co(CO)2Cp <200 °C Hexacarbonyld-butylacetylene dicobalt (Co-CCTBA) <200. . Ir Ir(acac)3 ~400°C Ni Ni(Et-NacNac)2 <~300°C Ni(RCp)-epirocarbodiimide (Ni(RCp)-pyrrolcarbodiminate), <~ 300°CR=alkyl Μη Mn(RCp) , R=alkyl>200°C Ru bis(2,6,6-trimethyl-cyclohexadienyl) 钌<350〇C Ru〇4 &lt ;150 °C Ru(Me-chd)(CO)3 ~225-250〇C Ru(Chd)(CO)3 ~225-250〇C Ru(EtCp)2 ~400°C Pt Pt(Me)3( MeCp) ~300°C Pt(Me)3(RCp) >200°C Cu Cu(R-NacNac)2, R=alkyl<200°C Cu(R-acNac)2, R=pit basis< 200 °C Cu(acac)(PR3)x, x=l-4, R=alkylate<250〇C Ti 肆(didecylamino)titanium (TDMAT) <275〇C 肆(ethyl Methylamino) titanium (TEMATi) < 275 〇C Ti_e2) (RCp), R = - or a plurality of alkyl groups < 325 〇 C Ti(OMe) 3 (RCp), R = - or a plurality of alkyl groups <400 ° C 12 201204860 The specific exemplary metal-containing precursors included in the structures listed in Table 1 include AlH3-NMe2Et, A1H3-decyl pyrrolidine, A1H2 (BH4), A1H2 (BH4): NMe3, and Cu ( Acac) [P(CH3CH2CH2CH2)3]2. The amine groups of the compounds can be independently substituted with one or more C! to C6 alkyl groups. Such exemplary metal-containing precursors are commercially available. The decomposition temperature of the metal-containing precursor in Table 2 of the applicant's letter is less than 500 ° C and may be lower than 400 ° C. Thus, the metal-containing precursors of Table 2 can also be used in the disclosed methods. The metal-containing precursors are commercially available or can be synthesized by methods known in the literature. Precursor precursor Mn(RCp)(CO)3, alkane Ir(EtCp)cod Ru(dimethylpentadienyl Ir(tmhd)3 RU3(CO)l2· IrF6 (toluene) (R-cyclohexane Rare) 钌,r=alkylbis(1-dimethylamino-2-mercapto-2-butoxy)nickel (MABO-Ni) Ru(aromatic)(diene) Ni(CO)4 Ru( Aromatic hydrocarbons (norborns) bis(1-dimethylamino-2-methyl-2-propanol) nickel [Ni(dmamp)2] Ru (aromatic) (cyclooctadiene) NiCp2 Ru( Aromatic hydrocarbons (butadiene) Ni(EtCp)2 Ru(CO)2-allyl Ni(MeCp)2 Ru(EtCp)(Me2Op) Ni(PF3)4 Ru(Me2Cp)2 NiCp(allyl) Ru (Me2〇p)2 Ni(allyl)(R-NacNac), R=alkyl Ru(MeCp)2 Ni(allyl)-R-pyrrolecarbodiimide, R=alkyl Ru( Od)3 Pd(Cp)COD Ru(tmhd)2(cod) Pd-allyl Ru(Cp)2 Pd(Me-allyl)2 13 201204860 Diborone Pd(Cp)allyl decane Pd ( Acac) 2 monodecane Pd(R-acNac) 2, R = alkyl diinthyl hoof __________ Pd(R-NacNac) 2, R = = alkyl dibutyl hydrazine (DffiuTe) .... Pd (Allyl) (R-NacNac), R = alkyl Sb (RO, R = Me and / or Et and / or iPr Au (R3P) C1, R = alkyl Te (R3), R = Me and / Or Et and / or iPr and / or tBu Au(CO)Cl [TeMe]2 penta(didecylamino) knob [PDMAT or (Me2N)5Ta] GeHxRv, xa〇,, R=alkylTiCl4 GeCl2: adduct (eg dioxane)肆(Dimethylamino)vanadium [TDMAV or (Me2N)4V] M0CI5 TaCl5 Mo(CO)6 TaCl5'SEt2 MoFe Third amyl imino-parade (dimethylamino) knob (ΤΑΙΜΑΤΑ) Mo ( Bz)(CO)3 Ethanol 钽(ΤΑΕΤΟ) Nb Ta(NtBu)(Me2)Cp NbCls TaFs Bis(1,3,5-trimethylbenzene) oxime tert-butylimido-diethylamine button TBTDET) Dimethylzinc... Bis(1,3,5-trimethylbenzene) button W(Bz)(CO)3 PtCp(allyl) wf6 Pt(PF3)4 WH2(RCp)2,R=alkane Pt(acac)2 Co(EtCp)2 Pt(C02)Cl2 CoCp2 Pt(Me)3Cp Co(R-NacNac)2, R=alkyl Pt(嫦propyl)2 Co(RCp)(脒基), R=alkyl Pt(Me)2COD Co(R-acNac)2, R=alkyl-based Cu(hfac)(PMe3) Co(acac)2 amine-alcohol steel Co(MeCp)2 Cu(hfac)2 double (2 ,6-Dimethyl-3,5-heptanedionyl) copper (Cu(D1BM)2) bis(1-dimethylamino-2-methyl-2-butoxy) copper (MABO-Cu )

14 201204860 _ t metal front. The body can be purely or in combination with the right! The blend of forms of metal (such as ethylbenzene monomethyl, 1'3,5-trimethylbenzene, decane, dodecane) can be present in different concentrations in the solvent. △ Pure or blended precursors are introduced into the reactor in vapor form by conventional methods such as piping and/or flow meters. The vapor form precursor can be produced by conventional vaporization steps such as direct vaporization, steaming, or by bubbling to vaporize the pure or blended precursor solution. Pure or blended precursor: is fed into the vaporizer in a liquid state, vaporized at the previous precursor, and then introduced into the reaction 2. Alternatively, the pure or blended precursor may be vaporized by passing a carrier gas through a coupler containing the precursor or by bubbling a carrier gas into a precursor. The milk may include, but is not limited to, Ar, He, A, and mixtures thereof. Any dissolved oxygen present in the pure or blended precursor solution can also be removed by bubbling with a carrier gas. The carrier gas and precursor are then introduced into the reactor as a vapor. If desired, the vessel containing the metal precursor can be heated to a temperature that allows the precursor to be in its liquid phase and have sufficient vapor pressure. The vessel can be maintained at a temperature in the range of, for example, from about 0 C to about 15 (Tc). Those skilled in the art recognize that the vessel temperature can be adjusted in a known manner to control the amount of precursor prior to vaporization. The reactor can be one in which the deposition method is practiced. Any closed chamber or chamber within the device, such as, but not limited to, a parallel plate reactor, a cold wall reactor, a hot wall reactor, a single wafer reactor, a multi wafer reactor, or other type of deposition Typically, the reactor contains one or more substrates on which the film will be deposited. The substrate is typically located on a susceptor or support pedestal within the reactor. Alternatively, the substrate may be located on the reactor wall, such as a column reactor. Seat, support pedestal or 15 201204860 can include heating and / or cooling components. Suitable heating components include heating lamps, lasers, induction heaters, mechanical heaters (heating plates, heating cups), infrared heaters, heating furnaces , a white heat heater, a flash anneal (fUsh annealei), a spike anneaier, or any combination thereof. The heating member can be close to the base, the support pedestal or the wall Contact with it. Suitable cooling methods include backside gas cooling or high velocity flow gas cooling. Backside gas cooling supplies cold air (such as liquid nitrogen, He, etc.) to the back of the substrate or susceptor or between the susceptor and the wafer. Cold inert gas (such as He,

Ar N2 4 ) is injected into the chamber to cool the substrate and possibly cool the chamber. An exemplary reactor suitable for use in the disclosed method includes a low profile dense atomic layer deposition reactor as disclosed in U.S. Patent No. 5,879,459, the disclosure of which is incorporated herein by reference. The apparatus has a substrate processing area adapted to enclose a substrate during processing and a retractable support pedestal extendable to the substrate processing area (Application of the invention further includes a substrate adapted to heat the substrate supported on the support pedestal) A heater and a cooling line for passing a coolant through a portion of the reactor (Patent No. 3). Another exemplary reactor that can be modified for use in the disclosed method includes the rapid disclosure disclosed in U.S. Patent No. 6,310,327. A thermal process reactor, the contents of which are incorporated herein by reference. The apparatus has a rapid thermal process reaction, a rotatable rapid thermal process susceptor installed in a rapid thermal process chamber, and is installed in a rapid hot process reaction chamber. Rapid thermal process radiant heat source (patent application scope item 1). The reaction chamber will need to be modified to include the precursor inlet. The rapid thermal process radiant heat source can be a plurality of lamps, each of which has a quartz-halogen lamp in 201204860. Application for patents Nos. 25 and 26). Equipment may further include installation in a rapid thermal process chamber Heaters under a rotatable rapid thermal process base, such as electric resistance heaters (patent 2 and 3). Rapid thermal process chambers may have water-cooled side walls, water-cooled bottom walls, and forced air-cooled top walls. Container combination (patent application scope item 23.) Unlike the radiant heat source installed outside the reactor, the laser or lamp array can be located on the base of the reactor. The recirculation cooler and temperature sensor can be located in the base. An exemplary reactor is disclosed in Figures 3 and 4 of U.S. Patent No. 7,6,393. The reactor can be a bell furnace with a vertical temperature gradient, wherein the bell jar top is better than the bell jar furnace. Bottom heat. One or more wafers may be located on the susceptor depending on the processing steps, which may move from the warm zone of the bell furnace to the cold zone. The 'reactor' may include two separate chambers, Introducing the metal-containing precursor into the first chamber at a lower temperature than the decomposition temperature of the precursor and saturating the surface of the substrate, and then moving the saturated substrate to a second chamber having a temperature higher than the decomposition temperature of the precursor. In this alternative Without cooling Because both chambers can be maintained at the desired temperature. The substrate located in the reactor can be any substrate suitable for manufacturing semiconductor, photovoltaic, flat panel or LCD-TFT devices. Examples of suitable substrates include (but are not limited to) a dream substrate, a oxidized substrate, a nitrided hard substrate, a gas oxidized substrate, a dummy substrate, or a combination thereof. Further, a substrate containing a crane or a noble metal (for example, gold) may be used. The substrate may also be deposited by a prior manufacturing step. Or a plurality of different material layers. In the disclosed method, the cycle adjustment reactor 17 201204860 according to the ALD process can be controlled by the temperature of the susceptor or as depicted in FIG.

Similarly, the temperature in the reactor can be maintained between about 2 Torr and about 400 ° C, preferably between about 5 ° C and about 300 ° C. As mentioned above, the temperature and pressure in the temperature. The reactor wall is controlled (i degree should be lower than the decomposition temperature of the metal-containing molecule. For example, for an AIH3 tertiary amine having a decomposition temperature of about 120 ° C, the temperature may be 1 〇 < rc. In another example, For a decomposition temperature of about 30 (TC of di-zinc, the temperature can be 275 ° C. The cavity-to-inner condition allows at least part of the metal-containing precursor to be deposited on the substrate or to saturate the substrate. Applicants believe that during deposition, the connection At least one ligand to the metal can be separated, and the metal is released to bind to the surface of the substrate in a process called adsorption/chemisorption. The temperature in the egg reactor is then adjusted and the pressure is adjusted as appropriate to make it The splitting of any residual ligand in the metal-containing precursor in the decomposition process only retains the metal bound to the substrate. Applicants believe that the temperature in the reactor is higher than the decomposition temperature of the metal-containing precursor. Sufficient conditions. Depending on the heating element of the reactor and the quality of the heat transfer, the temperature can be raised very quickly, possibly as short as a few milliseconds. Alternatively, the saturated substrate can be transferred from one chamber of the reactor to another. The chamber is used to adjust the temperature and pressure. Care must be taken to avoid heating the reactor to a temperature that will initiate a reaction between the remainder of the metal-containing precursor. These conditions can cause the resulting membrane to be exposed to undesirable impurities (such as C, N or hydrazine). Contamination. The temperature may be in the range of about 1 〇〇 〇 to about 18 201204860 l 〇 50 ° C, preferably about i 〇 0 ° c to about 6 〇 0 ° C. As mentioned above, the temperature should be higher than the metal containing molecules Decomposition temperature. For example, for an AIH3 tertiary amine having a decomposition temperature of about 120 ° C, the temperature may be 150 ° C. In another example, for a decomposition temperature of about 300 ° C, the temperature may be 4 〇〇 ° C. The pressure in the reactor can also be adjusted to further promote decomposition. The exemplary pressure is about 〇.〇! ((3 Pa) to about 2 〇〇 (26,664 pa), preferably about From 0.01 Torr (1_3 pa) to about 1 Torr (1333 Pa). The decomposition step (ie, at least raising the chamber temperature) can be performed simultaneously with the removal of any excess metal-containing precursor from the chamber. In the rinsing step, Remove any excess from the reactor by flushing with Nr Kb, Ar, He or a mixture thereof The metal precursor. Alternatively, the decomposition step can be carried out after rinsing. In the disclosed method, the formation of a metal film on the substrate does not require the use of a reactant. If a metal film having a desired thickness has been obtained, the process is completed. The process can be re-replicated until a film having the desired thickness is obtained. When the process is repeated, care must be taken to expose the wafer from above its decomposition temperature to below its decomposition temperature (ie, cooling step). The cooling rate is such that the wafer and the film thereon are not adversely affected by thermal stress. The cooling rate will be determined as appropriate, depending on at least the composition of the substrate, the number of two on the substrate, and the deposited metal film. After the thickness, the film can be further processed such as furnace annealing, rapid thermal annealing, sub-beam curing, and/or plasma gas exposure. Those skilled in the art are aware of systems and methods for performing such other processing steps. ‘~ Depending on the type of sediment deposited, the second precursor can be inserted into the reaction 19 201204860. The second precursor contains another metal source, such as 卩m,

Zr, Pb, Nb, Mg, A1, Ni, ^CU, Co, Fe, Mn, Ln, or a combination thereof may require the use of reactants (such as H2, NH3, 03, 02, etc.) to deposit a second inclusion on the substrate. Metallic Metals β When using a second metal-containing precursor, the resulting film deposited on the substrate may contain at least two different metal types. 0. The I metal # drive and any second metal-containing precursor, optionally selected. And/or reactants are introduced into the reaction chamber. The reaction chamber may be flushed with an inert gas such as H core, core or a combination thereof between the introduction of the precursor and the reactants selected in the second case. The vaporized precursor can be sequentially pulsed and any second metal-containing precursor, optionally selected, and optionally selected reactants. Each precursor pulse may last from about 0.01 seconds to about 10 seconds, or a period of from about 3 seconds to about 3 seconds or from about 0.5 seconds to about 2 seconds. The reactants optionally used may also be pulsed into the reactor. The pulse of each gas may last for about 10 seconds, or about 0.3 seconds to about 3 seconds, or a period of about 5 seconds to about ^ seconds. *Depending on the specific process parameters, deposition may be performed. Different lengths of time. Generally, the time required to sustain the production of a film of the requisite nature is required. The deposition process can also be performed as often as necessary to obtain the desired film. In a non-limiting exemplary ALD type process, the gas phase of the metal-containing precursor is introduced into a reactor having a temperature of 200 ° C and a pressure of 2 Torr (267 Pa), where it is contacted with a suitable substrate. The excess precursor can then be removed from the reactor by rinsing with Ns, Ar, He or a mixture thereof and/or evacuating the reactor at a pressure of 0.5 Torr (67 Pa). During the rinsing step or after the rinsing step, the reactor temperature can be raised to 5 〇〇t: and the pressure is raised to 3 Torr (_ (1). If the desired film is a metal film, the two-step process provides the desired film thickness The two-step process can be repeated until a film having a desired thickness is obtained. Alternatively, if the desired film is a bimetal film, the vapor pressure of the second metal-containing precursor can be varied in the above two steps. Up to about 4 Torr (TC, preferably about HHTC to about 35 (in the range of rc and pressure can be in about (four) Torr (1.3 PO to about 200 Torr (26,664 Pa), preferably about 〇〇 1 Torr (1 3

Pa) to reactor ten in the range of about 10 Torr (i, 333 Pa). A second metal-containing precursor will be selected based on the nature of the deposited bimetallic film. After the introduction into the reactor, the second metal-containing precursor is in contact with the substrate. Any excess second metal-containing precursor is removed from the reactor by flushing and/or evacuating the reactor. The reactants can be introduced to a temperature of about 300. The reactor is reacted with a second metal-containing precursor in a reactor having a pressure in the range of about 600 ° C and a pressure in the range of from about 0.01 Torr to about 200 Torr, preferably from about Torr to about 1 Torr. Excess reactants are removed from the reactor by flushing and/or evacuating the reactor. If the desired film thickness has been obtained, the process can be terminated. However, if a thicker film is required, the entire process can be repeated. A film having a desired composition and thickness can be deposited by alternately providing a metal-containing precursor, optionally a second metal-containing precursor, and optionally a reactant. When the plasma is used to treat the optional reactants in this exemplary ALD process, the exemplary ALD process becomes an exemplary PealD process. The reactants optionally used may be treated with a plasma prior to introduction into the chamber or after introduction into the chamber. 21 201204860 The metal film or bimetallic-containing layer produced by the above process may comprise pure metal (M) or bimetal (MWO film, such as metal citrate (MekSih), wherein k and 1 are in the range of 1 to 1 〇 Integers, including 1 and those of ordinary skill in the art, will recognize that the desired film composition can be obtained by proper selection of the appropriate disclosed precursor, optionally a second metal-containing precursor, and reactants. The following non-limiting examples are intended to further illustrate the specific examples of the present invention. However, the examples are not intended to be inclusive and are not intended to limit the scope of the invention described herein. Predictive Example 1 has the formula Ru(chd)(bz) The ALD deposition of the molecules needs to react with 〇2 to produce a film. However, 02 is not desirable for the application of Back End Of the Line (BEOL). Applicants have used the formula Ru(chd) The molecule of (bz) will produce a film without the use of ruthenium 2. Predictive Example 2 ALD deposition of a molecule of the formula Ru(chd)(CO)3 requires reaction with 〇2 to produce a film. However, 〇 2 is the back-end process (BE0L) should The use of a molecule having the formula Ru(chd)(CO)3 in the method disclosed by the applicant's letter will produce a film without using ruthenium 2. Predictive Example 3 CVD deposition of A1 molecule has been It is well known to us that the A1 film can be carried out using the A1 compound (such as AlH3.NMe2Et, A1H3.methylpyrrolidine and AlH2(BH4):NMe3) without using the reactants using the disclosed method 22 201204860. More specifically, the A1-containing precursor can be introduced into a reactor at a temperature of about 50° C. The excess precursor can be removed from the reactor by flushing with N 2 . The reactor temperature can then be raised to 150°. C. Applicant believes that the process will produce an A1 film on the substrate. Example 4 Place Ru(Me-chd)(CO)3 in a bubbler. Ensure carrier transfer with 50 sccm of A carrier gas flow. Maintain a bubbler pressure of 5 Torr (6,666 Pa) and room temperature. The reactor (6 〇 cm long hot wall chamber) is maintained at a constant pressure of about 0.7 Torr (93 Pa) with a constant specific flow rate. To maintain a steady pressure, enhance gas flow and rinse. A schematic of the reactor for deposition is depicted in Figure 1. TaN and The Ru substrate is placed in the chamber/furnace. During the introduction of Ru(Me-chd)(CO)3, the reactor temperature is fixed at 2〇〇c. After (co)3 is introduced at a time long enough to ensure surface saturation. (Introducing the precursor over a minute!), flushing the chamber with a stream. During the rinse, raise the reactor temperature to 5 ° C. At 5 〇 (after 1.25 minutes, the reactor temperature is lowered to 2 〇) (rc. Repeat the cycle to grow a film of defined thickness. The same experiment in which Ru(me_chd)(c〇) was entered on different substrates (TaN and Ru). The number of cycles is also different. The film thickness was measured by an ellipsometry method. Approximately 0.6 A/cycle was obtained on Ru obtained up to about 0.3 A/cycle rate on TaN at 6 sec. A slightly lower growth rate was found in only 30 seconds of precursor introduction 23 201204860, indicating that the surface saturation is incomplete. "It should be understood that the introduction time can be shortened by increasing the precursor flow rate and improving the reactor design to achieve faster surface saturation." . While the invention has been shown and described with respect to the specific embodiments of the present invention, it may be modified by those skilled in the art without departing from the spirit of the invention. The specific examples described herein are illustrative only and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Therefore, the scope of protection is not limited to the specific examples described herein, and is only limited by the scope of the following claims. [Simple description of the drawing] Fig. 1 is an explanatory form;

A graph of the relationship between the thickness of the tantalum film and the pattern of the cycle on the TaN substrate. Figure 2 is a diagram showing the thickness and circulation of the ruthenium film on the ruthenium substrate.

Claims (1)

201204860 VII. Patent Application Range: 1. A method for depositing a metal layer on one or more substrates, comprising the steps of: (a) introducing a metal-containing precursor pulse into a reactor in which at least one substrate is disposed, The temperature of the reactor is lower than the decomposition temperature of the metal-containing precursor; (b) saturating at least a portion of the surface of at least one of the substrates by at least a portion of the metal-containing precursor; and (c) raising the temperature of the reactor only A metal layer is formed on the at least one substrate up to a temperature higher than a decomposition temperature of the metal-containing precursor. 2. The method of claim 2, wherein the metal of the metal-containing precursor has an oxidation state of ruthenium. 3. The method of any one of the preceding claims, wherein the metal-containing precursor is selected from the group consisting of: (trisyl) (phenyl) crane [W (Bz) (CO) 3], (two bases) (phenyl) copper [m〇(bz)(c〇)3], (toluene) (cyclohexadiene) ruthenium, (cyclohexadiene) (tricarbonyl) ruthenium [Ru ( Chd)(c〇)3], (CO)丨2, (fluorenyl hexadiene) (tricarbonyl) ruthenium [Ru(MeCHD)(c〇)3] and bis(1,3,5-xylene ) 钽 and double (n% triterpenoid) 铌. 4. The method of any one of claims 2 or 2, further comprising repeating steps (a) through (c). 5. The method of any one of claims 1 or 2, further comprising (d) lowering the temperature of the reactor to a temperature below the decomposition temperature of the metal-containing precursor. The method of claim 5, wherein the temperature is lowered by cooling the back side gas or by high-speed flow gas cooling. 7. A metal layer ALD method, the method comprising: (a) setting a temperature of a reactor, the reactor comprising at least one substrate; (b) introducing a metal-containing precursor pulse into the reactor; (c) The surface of at least one of the substrates is saturated with at least a portion of the metal-containing precursor; and (d) removing at least a portion of the metal-containing metal only by raising the temperature of the reactor to a temperature above a decomposition temperature of the metal-containing precursor One portion of the precursor forms a metal layer on the substrate, wherein the metal concentration in the metal layer is greater than about 70 atomic percent, preferably greater than 90 atomic percent. 8. The method of claim 7, wherein the metal of the metal-containing precursor has an oxidation state of zero. 9. The method of any one of clauses 7 or 8, wherein the metal-containing precursor is selected from the group consisting of: (tricarbonyl) (phenyl) crane [W (Bz) (CO) 3 ], (tricarbonyl) (phenyl) molybdenum [Mo(Bz)(CO)3], (toluene) (cyclohexadiene) ruthenium, (cyclohexadiene) (tricarbonyl) ruthenium [Ru(Chd) (CO 3], Ru3 (CO) 丨 2, (methylcyclohexadiene) (tricarbonyl) ruthenium [Ru(Me-CHD) (CO) 3] and bis (1,3,5-triphenylene) button And bis (l,3,5-trimethylbenzene) oxime. 10. The method of claim 7 or claim 8 further comprising repeating steps (a) through (d). 11. The method of claim 11, wherein the temperature is lowered from step (d) to step (a) by cooling of the back gas 26 S 201204860 or by high-speed flow gas cooling. Eight, the pattern: (such as the next page) 27