TWI310967B - Method and deposition system for increasing deposition rates of metal layers from metal-carbonyl precursors - Google Patents

Description

1310967 IX. Description of the invention: [Related application for reference]

1 Ί Ί ΥΥ 说明 : : : : : 本 本 本 本 本 本 本 本 本 本 本 本 本 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 美国 MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET MET It is included here as a reference. This related eyelash is not shared. TECHNICAL FIELD OF THE INVENTION The invention relates to a semiconductor process, and more particularly, to a method and a deposition system for increasing the deposition rate of a metal layer by a pain s. [Prior Art] (4) In the manufacture of integrated circuits, it is necessary to expand the domain and growth of the people (4) and prevent (3) refractory materials, and mourn the town nn. The barrier layer/isolation layer deposited on the dielectric material may comprise materials which are non-reactive with Cu and the like, such as (4) and (4) Ta). Currently Cu metallization and dielectric materials

Ta layer or read a layer Jig two physical vapor deposition (10)) borrowed (10) w r ', continued TM Cu seed layer 'and then filled with electrochemical deposition at 1 wk f characteristics and selected Ta layer (as it is attached to prevent Cu Diffusion into; iow_k film ^ force, barrier characteristics and select Ta / M layer (such as U diffusion barrier materials are each with 'mutual;;: =:) and this 7 1310967 姥 (Rh) due to its expectations Behavior is similar to conventional refractory materials and has been identified as a possible barrier layer. However, compared to a two-layer structure such as TaAaN, 钌 (RU) or 铑 (Rh) = use of a permissible single-barrier layer This discovery is due to the adhesion and barrier properties of these materials. For example, a ru layer can replace the Ta/TaN barrier layer. In addition, recent studies have found that a Ru can replace the seed layer of (5), so it can be directly After the shame deposition, the bulk Cu is filled in. This discovery is due to the good practice between the Cu and Ru layers. The ruthenium layer can be pyrolyzed by the pyrolysis of the pre-loaded precursor, carbonyl ruthenium precursor in thermal chemical vapor deposition (TCVD). The formation of the material. When the substrate temperature is lowered to less than about 400 ^, the hunting is carried out by pyrolysis of the Ik-based precursor (such as Ru/CO» deposition The material properties of the ru layer deteriorate. Therefore, an increase in the reaction by-products mixed into the thermally deposited rib layer causes an increase in the resistivity of the Ru layer at a low deposition temperature and a poor surface morphological property (such as formation of nodules). The decrease in the desorption rate of carbon monoxide (C〇) from the carbonyl ruthenium precursor at pyrolysis at a substrate temperature of less than about 400 ° C can explain the above two phenomena. -, - In addition, due to the low vapor pressure of the carbonyl metal The problem of transport, the use of a metal carbonyl such as ruthenium carbonyl or ruthenium carbonyl can result in a low deposition rate. In summary, the inventors have observed that current deposition systems are not feasible for deposition of such metal films at low deposition rates. SUMMARY OF THE INVENTION The present invention provides a method and a deposition system for increasing the deposition rate of a metal layer from a metal carbonyl precursor. Embodiments of the present invention can increase the vapor temperature of a metal-containing precursor to increase a carbonyl group. The vapor pressure of the metal precursor, thereby increasing the vapor of the metal carbonyl precursor delivered to Luli and increasing the rate of metal deposition on the substrate. The real thing is to make the GG gas metal precursors age, to prematurely solve the carbonyl metal precursor vapor before the carbonyl metal vapor contacts the substrate. In addition, the dilution gas is added to the processing gas to process and reduce the vice The shame gas is used to treat the partial pressure of the wipe. Therefore, the method comprises: providing a substrate in the processing chamber of the deposition system; the shape 1310967 is formed to contain a metal carbonyl precursor vapor and the co gas body is introduced into the processing chamber, - a diluent gas plus a gas on the substrate by means of a finely diluted process gas. The solid material of the present invention has a general formula & drive. The metal carbonyl includes but is not limited to: w (e condensed base metal is 0 〇, (00> - Rhl(C0), 2 ^ Re^CO),, ^ ' method, by: in deposition ====

芙二. From Uf, a substrate containing - or a plurality of through holes or channels or a combination thereof, is introduced into the processing chamber from a rU3 (co) 12 gas stripping gas and a co gas forming process gas; The gas is added to the process gas to expose the deformed substrate to the diluted process gas volume Li, and the surface is deposited on the substrate.

Hi* board support for supporting and wire-feeding plates with a vapor distribution system, the precursors are used to (10) into a process gas comprising a ship's vaporizer and (3) gas to pass the process gas The source of the dilution gas is used to: the diluent gas is added to the treatment chamber and the controller is used to expose the substrate to the diluted process gas to be heated by the chemical gas. Phase deposition county deposits a metal layer on the substrate to control the deposition system. [Embodiment] j In order to facilitate a full understanding of the present invention and for purposes of explanation and not limitation, specific details such as the particular geometry of the deposition system and the description of the system components are described in the following. However, it should be understood that the invention may be practiced otherwise by other embodiments. Where appropriate, similar reference numbers are used to indicate similar features. 1310967 The silk metal Fuling substrate is sun-dried on the substrate. The processing, the --phase drive transport system 40 is connected to the metal precursor evaporation system processing chamber 10 and is connected to the vacuum 38 40 and the metal fines 5Q to the genus layer by the transfer tube 36, and In the metal precursor evaporation line 5G Anxian County Jinqi ^ Cheng drive 2 drive f evaporation system 50 series used to store several base metals before A Λ 2 heated enough to steam brittle metal precursors t ^ silk tree, gambling _ Pure 4 (four) temperature. The gold t precursor 52 can be a liquid. The solid tiff will be described below. However, those skilled in the art should note that they do not leave the drive. For example, the subordinate precursor may have the general formula 可 and can be = gold = ^, several base! mesh, silk aunt, county fault, county chain, county chrome, silk-based iron, or Μοί〇1 Cmf ship genus contains but not The limit is: W(C0)6, Ni(four)4, ff〇)l2 'Re2(C〇)l° 'Cr(C0)6 'Ru3«°)12 ^ 0s3(C0)i2 or a combination of two or more thereof . The rib metal precursor 52 evaporates (or the money-based metal precursor enthalpy temperature, the metal precursor evaporation system 50 is connected to control the secret, the degree control system 54. For example, for the sublimation silk 钌 (4) (10) 2, the know-how The temperature of the precursor 52 is raised to about ≤ 45 C. At this temperature, the evaporation pressure range of 'Ru3(10)12 is, for example, from about} to about 3 mTorr. Although the metal carbonyl precursor is heated to evaporate (or sublimate), The carrier gas can be moved over or over the I-based metal precursor 52 or a combination thereof. The carrier gas can include Example 1310967, and the inert gas 'such as the rare gas He, Ne' red, or k' can be omitted in other embodiments. The carrier gas '5' is actually a gas towel. Or in its tube (4) to === square gas = 60 to the self-metal precursor fresh system supply system ίί;: the vapor of the precursor 52 enters the gas phase precursor The gas delivery system has a gas supply to the base metal precursor 52. Although the hole is not shown, the gas supply system 6〇 may include: With control room, - or multiple transitions, and quality two = for example, load = amount can be between About 标准·! Standard cubic centimeters per minute (sccm) to about ^^ The carrier gas flow rate may be from about 1 G coffee to about 5 〇G sccm. Or alternatively, about 5 G _ to about the measurement. According to an embodiment of the present invention, The range of C〇ff ranges from about 0.1 to about 1000 scon. Alternatively, the 'gas amount of co gas can range from about 1 seem to about 100 sccm. 下游f metal precursor evaporation system 50 downstream, containing carbonyl metal precursor = the gas passes through the gas phase precursor delivery system 4〇 until it enters the processing chamber by connecting to the production system. In order to control the temperature of the vapor line and prevent the decomposition and condensation of the secret metal precursor The gas phase 40 can be connected to the vapor line temperature control system 42. The delivery system is 'washed again' with reference to Figure 1, which is a portion of the processing chamber 10 of the vapor distribution system 3 Λ 10 if containing: the distribution of the wire chamber 32, The vapor is dispersed in the vapor distribution plenum before the vapor passes through the vapor distribution plate 34 into the treatment zone 33 on the substrate 25. In addition, the vapor distribution plate 34 can be connected to the temperature control system for the distribution plate. 35. City I, / dish according to an embodiment of the invention, dilution gas The source 37 is connected to the processing chamber and is used to add a diluent gas to dilute the 1310967 containing the metal carbonyl precursor vapor and the C 〇 gas. As shown in FIG. 1, the diluent gas source 37 can be fed through the feed line 37a. The diluent gas is added to the process gas in the vapor distribution plenum 32 before the treatment passes through the vapor distribution plate 34 and into the zone 33. Alternatively, the diluent gas source 37 can be fed by Line 37b is coupled to process chamber 10/for use to add diluent gas to process gas in process n 33 above helium 25 after the process gas has passed through vapor distribution plate 34. Still alternatively, the diluent gas source can be connected to the vapor distribution system 3〇 by a feed tube, line 37c, and used to dilute the gas

Processing gas in ϊί 34. Those skilled in the art should note that the diluent gas may be added to the process gas at the vapor distribution system 3 and elsewhere in the process chamber from this month. Once the processing gas containing the silk metal precursor vapor is processed, the box precursor vapor adsorbed on the surface of the substrate 33 will immediately become a metal phase in the field of the substrate 25 due to the rise of the temperature of the substrate 25. The 20 series is used for its advantage by being connected to the substrate temperature control system 22. For example, the substrate temperature control system 22 can be used to raise the pitch up to about 500T. In addition, the processing chamber 10 can be connected to the body temperature control of the body. The control chamber wall temperature is, for example, as described above, and the conventional system considers: for Ru3 (c avoids pyrolysis, in the temperature range below about the pyrolysis temperature, about 仞^ to ^2, for the precursor evaporation system 50 and the gas phase precursor The material transport system 4〇. The inter-L operating metal can be pyrolyzed at elevated temperature to form by-products, as shown below, such as 'Ru/co)! 2 Ru3(C0)i2 (ad) <=> RusCCOX (ad) + (12~χ) CO^C )' or g (1)

Rii3(C0)x (ad) 3Ru(s) + x CO (g) where these by-products can be adsorbed or condensed) to the surface of the surface (2). The material accumulated on these surfaces can be repetitive on the substrate and the internal surface of the substrate 1). Or, for example, Ru3(CO)i2 can condense in the Shensuluo bow problem (eg, on the inside surface of the system 1)

Ru3(C0)i2 (g) <^> Ru3(C0)i2 (ad) (3) 12 1310967 In summary, certain carbonyl metal precursors (such as low vapor pressure and narrow process window) result in the substrate Very low metal deposition rate on 25. Related US Patent Application No. 10/χχχ, χχχ, its invention name

"METHOD FOR INCREASING DEPOSITION RATES OF METAL LAYERS FROM METAL-CARBONYL PRECURSORS", and applied for on the same day as the case, the inventor including the application of this application should understand that: (7) gas is added to the carbonyl metal before the vapor can be reduced The above problem of transporting the metal carbonyl precursor to the substrate is limited. In accordance with an embodiment of the present invention, co gas is added to the metal carbonyl precursor vapor to reduce decomposition of the metal carbonyl precursor vapor in the gas line, thereby shifting the equilibrium in the reaction (1) to the left, and The reduction of the 13⁄4 base metal in the gas phase precursor delivery system, such as the precursor, is prematurely decomposed before being delivered to the processing chamber 10. It is generally believed that the addition of C0 gas to the metal carbonyl precursor vapor can increase the gasification temperature from about to about 150X, or higher. The elevated temperature increases the vapor pressure of the metal carbonyl precursor, resulting in an increase in the metal carbonyl precursor delivered to the processing chamber, thereby increasing the rate of metal deposition on the substrate 25. Further, the inventors have personally observed that the passage of the mixed gas of C0 and the passage of the metal carbonyl precursor can reduce the premature decomposition of the metal carbonyl precursor. Sheet According to one embodiment of the invention, the addition of C0 gas to the Ru/COh precursor vapor allows the temperature of the precursor vapor of Ru3(C0)i2 to be raised from about 4 〇〇c to about 150 °C. Alternatively, the vapor temperature can be raised from about 60 DC to about 90 °C. <α<Generally, 'by removing co and desorbing CO by-products from the substrate 25, the pyrolysis of the metal carbonyl precursor and the subsequent deposition of metal on the substrate 25 proceed smoothly. During the deposition period, the C0 job is mixed into the metal layer due to incomplete decomposition of the precursor metal precursor, incomplete removal of the C0 by-product from the metal layer, and (7) byproducts from the treatment chamber are again adsorbed on the metal layer. To. It is believed that the incorporation of C0 by-products into the metal layer during deposition causes the coarse surface of the silk surface to be revealed in the form of the nodules of the metal layer t, where the growth of the nodules is enhanced by the increase in (1) the incorporation of by-products into the metal layer. Further, (7) the by-product mixed metal layer increases the resistivity of the metal layer. 13 1310967 == Byproducts are mixed into the metal layer by (1) reducing the processing pressure and (2) increasing the substrate temperature. It has been known in the present invention that it is also possible to reduce the problem: a diluent gas is added to the containing metal C in the processing chamber 10. In the gas processing gas, the ribs control and reduce the partial pressure in the by-products and c〇. Therefore, according to an embodiment of the present invention, the gas from the lean body, 37 is added to the gas injection to (4) and the partial pressure of the metal by-product and the co-pressure in the processing chamber 10 are reduced, thereby forming a smoothing. The golden surface. The gas may include, for example, an inert gas such as a rare gas He, J: Kr or Xe ' or a combination of two or more thereof. The diluent gas may further comprise a gas to improve the material properties of the metal layer, such as electrical resistivity. The reducing gas ^ column ^ contains H2, containing a gas (such as SiH4, secret or 2ίί2), a boron-containing gas, β^) or a nitrogen-containing gas (such as leg 3). According to an embodiment of the invention, the pressure of = may be between about G.1 mTarr to about Hiroshi. Alternatively, the pressure may be between about 丨mTorr and about mT〇rr. Still alternatively, the process chamber pressure can be between about 2 mTorr and about 50 mTorr. Second, the addition of the C〇t body to the base metal precursor vapor increases the thermal stability of the base metal gas, so the vapor readout of the silk metal precursor in the process gas is higher than that of the available wire substrate. The decomposition rate of ίίΐί. In addition, temperature can be used to control the metal on the substrate and thus control the rate of accumulation. It is well known that (4) the age of the person: the amount of the reading and the substrate temperature, the evaporation of the metal precursor of the diamond, and the desired deposition rate of the metal precursor on the substrate 25. n T selects the amount of C0 gas in the process gas such that the metal from the precursor on the substrate 25 is deposited in the power limiting temperature range. For example, the amount of gas in the middle can be increased until the metal deposition process is observed to occur in the dynamic temperature range. The dynamic limit temperature range refers to: - a specific deposition strip and the chemical chemistry in the chemical vapor deposition process limited to the surface of the substrate. 1 is generally characterized by a strong correlation between deposition rate and temperature. Not like the temperature range of the t, usually the mass transfer limit is observed at higher substrate temperatures. 1310967 Reaction: Transmission; the deposition rate in the range is limited by the chemical rate. The base metal precursor flow is strongly correlated with the presence of a good metal layer. Conformal. Usually "=艮? _ white ladder coverage divided by the metal bottom (4) cover leaving the feature (the thickness of the metal layer on the bottom = system Ϊ 1 can also include rib operation and control deposition system 1 2 〇 连 翁 胄 1G , substrate support 3 〇, gas phase forward delivery system / = = = 21 gas distribution system source 37 and gas supply system 6 〇. Metal then evaporator evaporation system 50, dilution gas sinking season 2 = in the other two = column The middle rib deposits a metal film such as a substrate support 120 on the substrate, and a metal layer is formed on the substrate. The process ί 105 ? 1〇5 ίίί evaporates the metal precursor of the precursor 152 The system m and the system are transported to the processing chamber, and the gas phase precursor transport processing to 110 includes: an upper chamber 1H and a lower chamber 1 2 = 14 are formed in the chamber 112 from the lower portion of the gate; Connected to the exhaust chamber 113. Where r Η strands to 112 Still referring to Fig. 2, the substrate support 120 provides a horizontal surface to go to #卢12530125 ° from the lower portion of the fourth chamber 113 to the upper portion of the i-shaped branch ^ The support substrate holder is ^22. In addition, the substrate support 120 includes a heater 126 that is coupled to a plate or temperature control system 128. The heater 126 can be packaged, for example. - or a resistive heating element, field_light. Substrate support temperature control system 128 15 1310967 may include a power supply for supplying power to - or a plurality of heating elements; for measuring substrate temperature, substrate support Temperature or a temperature of both - or a plurality of temperature sensors; at least one of the substrate temperature or the substrate support temperature is applied, controlled, adjusted, and the heated substrate 125 is pyrolyzable The base metal precursor base metal is deposited on the i-plate 125. According to an embodiment, the metal carbonyl front: 152 may be a number of base precursors, for example, 々0-(iv)i" well-known thermochemical vapor deposition technique Note: t: Other filament drives are not heated. The substrate holder 120 is heated to a predetermined temperature suitable for depositing a desired Ru metal layer or a metal layer thereof onto the substrate 125. A heating n (not shown) connected to the cavity g temperature control system 121 can be embedded in the wall of the processing chamber 11 () to heat the chamber wall to a predetermined temperature. The heating || can be used to treat the wall of the chamber , or from about hunger to about to jump. Dust force meter (not shown) is used to measure to pressure According to an embodiment of the invention, the pressure in the processing chamber may be between 0.1 mTorr and 200 mTorr. Alternatively, the pressure in the processing chamber may be between about i mT 〇 rr and 100 m Torr. Alternatively, the pressure in the processing chamber may be Between about 2 rainbows and mTorr. That is, as shown in Figure 2, the vapor distribution system 130 is coupled to the chamber ί3 of the processing chamber 11. The vapor distribution system 130 includes a vapor distribution system 132 for dispensing the plenum 132 from the vapor. A plurality of orifices 134 are passed into the vapor distribution plate 131 of the processing zone 133 above the substrate 125. According to the present invention, in the embodiment, the diluent gas source j37 is connected to the processing chamber j1 system 13〇Hx in the processing area of the processing gas passing through the vapor distribution plate 131 into the substrate above the inspection zone. The process gas body/f 137 that can be used to add the diluent gas to the vapor distribution plate 131 through the feed H line 137c can be connected to the processing chamber and used to process the gas. After m is matched, after 131, the diluent gas is added to the processing zone 133 by the feed line leg. Those skilled in the art should be able to add diluent gas to other locations in the processing chamber 110. For example, Ιίϋ a few base metal precursors decompose or condense. For example, a liquid system t138 can be supplied to the liquid conduit. The vapor distribution temperature liquid, the field source, the heat exchanger; or a plurality of controllers for measuring the temperature of the knife plate 131 controlled from the sphincter to about 15 〇〇c. m Precursor gold emitter flooding secret (10) _ to support the county metal: the base of the genus precursors and bribe metal precursors ΐί Hua) ° precursor heater 154 is used to add _ base metal before the temperature. The precursor heater 154 is coupled to an evaporative temperature control system 156 for controlling the temperature of the 152. For example, the precursor heating 1°_54 can be used to adjust the temperature of the base metal precursor 152 from about hunger to about 15 〇C, or from about 60 ° C to about 9 (TC. #When heating the base metal precursor 152 to When it is evaporated (or sublimed), the flow can be passed over or through the hot metal carbonyl precursor 152, or any combination thereof. The carrier gas can comprise, for example, an inert gas such as a noble gas (eg, He, Ne, red, stove) 1): Alternatively, other embodiments contemplate omitting the carrier gas. According to one embodiment of the invention, the gas may be added to the carrier gas. Alternatively, other embodiments contemplate replacing the loading with an omega gas. For example, gas supply System 160 is coupled to metal precursor evaporation system 15A and is used, for example, to flow carrier gas 'CO gas or both across or through metal carbonyl precursor 152. Although not shown in Figure 2, gas supply system 16 The gas phase precursor transport system 140 can also be/or coupled to supply carrier gas and/or (3) gas to the metal carbonyl precursor at or after the vapor of the metal carbonyl precursor 152 enters the rolling phase precursor delivery system 140. Vapor of 152. Gas supply system 16〇 may include a gas source 161 comprising 17 1310967 carrier gas, co gas or a mixture thereof, one or more control valves 162, one or more filters 164, and a mass flow controller 165. For example, a carrier gas or c The mass of the helium gas/the amount of the melon is from about 0.1 sccm to about sccm. In addition, the sensor 166 is arranged to measure the total gas flow from the metal precursor burst system 15〇. 166 may, for example, comprise a mass flow controller, the sensor 166 and the mass flow controller may determine the amount of vapor before delivery to the carbonyl fund of the processing chamber 11. Alternatively, the sensor 166 may include a light absorbing sensor to The concentration of the metal carbonyl precursor in the gas stream to the processing chamber 10 is measured. The bypass line 167 can be located downstream of the self-sensor 166 and

The substance transfer system w is connected to the exhaust line 116. The bypass line 167 is provided with ^== 140, and is used to stabilize to the processing chamber 10 of ^^, , °. Further, the bypass valve 168 is located downstream of the branch of the gas phase precursor delivery system 140 and is disposed above the bypass line 167. Knife ★, referring to Figure 2, the gas phase precursor delivery system 14A includes a vapor line having a first valve 141 that conducts vapor. In addition, the gas phase precursor delivery system 140 is incorrectly used by the ageing (not shown) to heat the vapor phase precursor delivery system. The temperature of the controllable relay line is 100 C ' or from about 4 (TC to about 9 〇. ( ). System 2 2 supplies (1) gas to the system (10). For example, the gas supply delivery system 140, and For example, the county gas precursor system 190 in the co gas/gas-夂-precursor transport system may include: a C gas source (9), one or more gas 1 masses - A multi-T ferrite 194, and mass flow control. For example, the circumference may be from about G.1 sccra (standard cubic centimeters per minute) to 〆+mass flow controllers 165 and 195, and valves 162, 192, 168, 141 14? by controller 196 Control, 兮 batch 5 | batch also 丨 version, 141 and 142 gas and identify the control (10) control to do, stop and carrier gas, C0 hole body and rebel metal secrets money flow. Sense 166 is also connected to The controller 1310967 196 'and the controller 1% can control the carrier gas flow according to the sensor ι 66 165 to obtain the expected mass flow, and control to the processing chamber 110. The base metal is driven by the flow 1 as shown in FIG. It is shown that the exhaust line 116 connects the exhaust chamber 113 to the real system 119 system for evacuating the processing chamber to the desired office, and the self-processing during the period The chamber 110 removes the aerosol species from the #^ degree' and uses the inter-butter or inter-valve valve. The collector 117 can collect unreacted precursor material and by-products from the processing chamber 110. Referring back to the processing chamber 110 The substrate holder 12〇, Sf2^ ΐmb two substrate lift locks 127 are fixed to the plate 123 and can be lowered to a position below the upper surface of the substrate support 20. A drive mechanism 129 utilizes, for example, a cylinder 200 and a Mit2f2W. 5 can be transferred into and out of the processing chamber 110 via the interval valve (4) 7f, and lifted for the substrate, 127. Once the substrate 125 is received from the transport system, it will descend and lower the substrate to the upper wire of the substrate support 120. Close 127 into the private η,,, Figure 2 'Controller 180 contains: microprocessor, memory and digital output ^ output interface. The digital wheel input and output interface can be generated to communicate and activate the process of the input signal two: : = output of the system 1GG ^ In addition, the consumption control system (4) (10) can be connected ^ 3 = system T controller 1%, vapor line temperature control system 143 and steam = degree control system 156 before the transport system 1G5; steam Distribution temperature control. 8 L vacuum suction system, system 118 and wire bearing temperature control System 128, and can exchange information. In vacuum pumping system 118, controller 18 is coupled to an automatic pressure controller 115 that controls the pressure of process chamber 110 and exchanges information with it. 19 1310967: Stored in (4) (4) Shout Available Saki _ Syrian shout

Iso W II, Division (Dell C〇rporation, Dallas, Texas) Legs w〇RkSTaTMN 610TM. The controller 18 can also be implemented by a common shame, digital signal processor or the like. The controller 180 can be placed adjacent to the deposition system (10) or it can be located at the distal end of the 3 deposition system (10). Therefore, the controller ‘ Γ Γ f data. The controller 180 can be connected to a client (such as a device manufacturer, or can be connected to an internal network of the provider side (such as a machine manufacturer). And at another l computer (such as a controller, a server) The controller can be used to exchange data by at least one of a direct connection, an internal network, or the Internet. 3 is a method of depositing a metal layer on a substrate according to the present invention. 300 includes the process of providing the substrate to the deposition system in step 302. For example, the deposition system may include the above-described figures i and =, and the board may be a substrate, and according to the type of skirt formed, the mis-g is n. Substrate. According to an embodiment of the present invention, the substrate may be a patterned substrate including a via, or a trench, or a combination thereof. In step 304, a processing gas of a base metal precursor vapor and a CG gas is processed. According to the embodiment, the base metal precursor may be several ϋΐ 2RU 3 The elevated temperature can increase a few bases == ί; Adding to the processing chamber increases the deposition rate of the metal on the substrate. The example of the process gas can be processed by adding a base metal precursor, steam, and a gas-free metal-free precursor. Vapor 3 In the present invention, a gas of 0 can be mixed with a carbon-based metal precursor vapor downstream of a few base metal precursors. According to another embodiment of the present invention, a 20 1310967 F group can be additionally used to carry a carrier gas. Flow over or through the base of the brittle base metal precursor gas distribution cup and hold it into the J! i figure, after the process gas can pass through the middle of the process, the lion gas can be added To the vapor separation ". Or, can be gas phase red turn-shaped" "by thermochemistry = plate 4 application, cocoa between about 30 (TC to 400 ° C., genus or substrate temperature contains The step or stage may be: f' 304 ' 306 '308 ^ ^ 30. The t-type f-plate can be implemented to include one or more through-holes. The present invention is based on the present invention. FIG. 4A is in accordance with the present invention. The embodiment generalizes the substrate on the structure 400. The patterned structure 4 includes a layer 44 The patterned layer 420 is deposited into the patterned mouth. Example 1, the metal layer 410, and the open opening 430 may be a through hole or a trench, and the f 20 may be a dielectric material. For example, the figure is fine. The other "!= genus layer/may contain this metal. 匕3 opening. The barrier layer gamma is deposited on the rounded structure 1310967. The metal layer 460 is deposited on the barrier layer 450. For example, the barrier layer 450 or a germanium-containing material (such as Ta, TaN, or TaCN, or a combination of two or more thereof), an opening: (such as W, WN). For example, the patterned layer can be a dielectric material. For example, Figure 4r&gt ;r can be a via or a trench, and for example, the metal layer 460 can comprise a Ru metal. The deposition of Cu in opening 430 of Figure 4B is shown. It is to be understood that the following is a description of the several embodiments of the invention, and it is understood that the invention may be practiced or modified without departing from the novel teachings and advantages of the invention. Therefore, all such modifications should be included in this issue.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a deposition system in accordance with an embodiment of the present invention. 2 is a side view showing a deposition of a metal layer according to another embodiment of the present invention, and FIG. 3 shows a schematic diagram of a metal layer deposited on a substrate on the substrate according to an embodiment of the present invention. FIG. 4C is based on FIG. Forming a metal layer to a patterning base according to an embodiment of the present invention [Main element symbol description] 1 : deposition system 10: processing chamber 12: chamber body temperature control system 20: substrate holder 22: substrate temperature control system 25 • substrate 30 : Vapor distribution system 32: Vapor distribution plenum 33: Treatment zone 22 1310967 34 · Vapor distribution plate 35: Dispensing plate temperature control system 36: Delivery pipe 37: Dilution gas source 37a, 37b, 37c: Feed line 38: Vacuum pumping System 40: gas phase precursor delivery system 42: vapor line temperature control system 50: metal precursor evaporation system 52: metal carbonyl precursor 54: evaporation temperature control system 60: gas supply system 61: feed line 62: feed line 63: Feed line 80: control system 100: deposition system 105: precursor delivery system 110: processing chamber m: upper chamber 112: lower chamber 113: exhaust chamber 114: opening 115: automatic pressure control (APC) 116: exhaust line 117: collector 118: vacuum pumping system 119: vacuum pump 120: substrate holder 23 1310967 121: chamber temperature control system 122: cylindrical support member 123: plate 125: substrate 126: Heater 127: substrate lift pin 128 · substrate support temperature control system 129 : drive mechanism 130 : vapor distribution system 131 : vapor distribution plate 132 : vapor distribution plenum 133 : treatment zone 134 : orifice 137 : dilution gas source 137a Feed Line 137b: Feed Line 137c: Feed Line 138: Steam Distribution Temperature Control System 140: Gas Phase Precursor Delivery System 141: First Valve 142: Second Valve 143: Steam Line Temperature Control System 150: Metal Precursor Evaporation System 152: metal carbonyl precursor 154: precursor heater 156: evaporation temperature control system 160: gas supply system 161: gas source 162: control valve 24 1310967 - 164: filter 165: mass flow controller 166: sensor 167 : bypass line 168: bypass valve 180: controller 190: gas supply system 191: CO gas source / 192: control valve 194: filter 195: mass flow controller 196: controller 200: gate valve 202: cavity access channel 300: method of depositing a metal layer on a substrate 302: providing a substrate to a processing chamber 304 of a deposition system: forming a processing gas 306 comprising a metal carbonyl precursor vapor and a CO gas: adding a diluent gas to Process gas 308: exposing the substrate to the diluted process gas to deposit a metal layer 400 on the substrate by a thermal chemical vapor deposition process A: patterned structure 402: patterned structure 420: pattern layer 430: opening 440 : metal layer. 460: metal layer 25

Claims (1)

1310967 Patent Application No. 94142050 Patent Application Revision (without scribe lines) X. Patent Application Scope - 1. A method for depositing a metal layer onto a substrate, comprising the steps of: providing a substrate to provide a substrate to a processing chamber in a processing system, wherein the processing chamber includes a vapor distribution system adjacent an inlet of the processing chamber, and a processing zone between the vapor distribution system and the substrate. The vapor distribution system includes a vapor distribution plate adjacent to the treatment zone, and a vapor distribution plenum located between the inlet and the vapor distribution plate; a process gas forming step of forming a package by using the following steps (j Exchanging vapor and one of the carbon monoxide (C〇) gases to treat the gas: heating a solid carbonyl metal precursor in a precursor evaporation system to form the Wei-based metal precursor vapor, and heating the CO The gas flows to be in contact with the precursor evaporation system, the HI body carbonyl metal fines of the precursor, to the metal carbonyl metal when the county metal precursor = gas formation The precursor vapor captures the process gas of the C gas to pass the step of 'the process gas from the precursor evaporation system A thermal chemical vapor deposition process deposits a metal layer onto the wire. Law, between. Seem to about 1〇〇〇 sccm Please use the _丨 item to sink the metal layer on the substrate. The flow of the CO gas is between about 1 seem and about 1 〇〇 sccm. 26 1310967 A method of depositing a metal layer onto a substrate according to item 1 of the wood patent range, wherein the process gas forming step further comprises: passing a carrier gas over or through the metal carbonyl precursor. And = a method of depositing a metal layer onto a substrate according to item 4 of the patent application, wherein the carrier gas contains a rare gas. 6. A method of depositing a metal layer onto a substrate as in claim 4 wherein the flow rate of the carrier gas is between about 0.1 seem and about 1000 sccm. 7. For example, the method of depositing a metal layer onto a substrate according to the first aspect of the patent, wherein the base metal precursor vapor comprises: a tungsten carbonyl, a molybdenum carbonyl, a cobalt carbonyl, a ruthenium carbonyl, a ruthenium carbonyl. Or a carbonyl hydrazine' or a combination of two or more thereof. 8. A method of depositing a metal layer onto a substrate as claimed in claim 1 wherein the carbonyl metal precursor vapor comprises: W(CO)6, Mo(CO)6, Co2(CO)8, Rh4(CO)12, Re2(C〇)10, Cr(CO)6, Ru3(CO)i2, or 〇S3(CO)i2 'or a combination of two or more thereof. 9. The method of depositing a metal layer onto a substrate according to claim 1 of the patent application, further comprising: maintaining the substrate at a temperature of between about 50 ° C and about 500 ° C during the 5 MW substrate exposure step between. 10. The method of depositing a metal layer onto a substrate according to claim 1 of the patent application, further comprising: maintaining the substrate at a temperature of about 27 1310967 300 ° C during the step of the substrate turbulence step. 400 ° C. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; 0·1 mTorr to approximately 200 mTorr. 12. The method of depositing a metal layer onto a substrate according to claim 1 of the patent application, further comprising: φ maintaining the processing chamber at a level of about 7^7 lm to about 1 于 during the substrate exposure step 〇mTorr. The method of depositing a metal layer onto a substrate according to claim 1, further comprising: maintaining the processing chamber at a pressure between about 2 mTorr and about 50 mTorr during the substrate exposure step . 14. The method of depositing a metal layer onto a substrate according to claim 1, wherein the diluent gas addition step comprises: adding the diluent gas to the processing gas in the vapor distribution plenum; and The diluted gas flows through the helium distribution plate of the vapor distribution system to the treatment zone. a method of depositing a metal layer onto a substrate according to claim 1, wherein the diluent gas addition step comprises: after the process gas flows through the vapor distribution plate, the diluent gas is treated in the process Add to the processing gas. When the 1310967 month ~ 曰 correction replacement page λ (- Pingyue ~ day 1 method, ^ slave deposits the money layer to the substrate i of the eight Τ 亥 稀释 dilution of the milk addition step contains: add the dilution gas The method of treating the gas in the vapor distribution plate (10). The method wherein the dilution gas layer is deposited on the substrate -==3⁄4 layer deposited on the substrate ===(4) 1 domain on the substrate or 2 a plurality of, a body, a body, or a gas containing 1, or a method of depositing a metal layer onto a substrate of the first or second method of the substrate The method of claim 1, wherein the process gas forming step further comprises: a /, utilizing the base metal precursor vapor on the earth plate relative to the c Controlling the distribution of the metal precursor on the substrate A method of depositing a metal layer onto a substrate. A method of depositing a metal layer on a patterned substrate, including a method of depositing a RU metal on a patterned substrate, Step 1310967: a patterning base subtraction step of providing a patterned substrate to a processing chamber of a deposition system, the patterned substrate comprising - or a plurality of vias or trenches, or And wherein the processing chamber includes a vapor distribution that is adjacent to the inlet of the processing chamber, and a processing region located between the button and the substrate, the system partition (4) including adjacent to the surface a vapor distribution plate, and a venting chamber between the person σ and the distribution plate; ..., a treatment gas forming step, using the following steps to form a precursor vapor and a carbon oxide (CO) gas - treatment gas: , plus the precursor of the precursor Ru3 (c〇) i2 in the precursor evaporation system to form the Ru3 (CO) 12 precursor vapor, and two on the heating day ^, the CO gas flows With the precursor evaporation system, Qiao, Ru3 (CO) 12 precursor contact 'to generate the Ru3(c〇)i2 precursor tomb milk ^• capture the Ri^COL precursor vapor into the c〇 gas: value into the step 'the (10) 1 ^ the precursor evaporates System Ϊ 该 the inlet, the process gas is passed through the vapor distribution system, and is passed into the processing zone of the processing chamber; a plate and a step 'in the vapor distribution plenum, the vapor distribution plate, the process &amp; At least one of them, a diluent gas is added to the process gas to form a diluted process gas in the process chamber; and is accumulated on the wire plate. A method of depositing RU metal on a patterned substrate in accordance with item 23, wherein the flow of the C0 gas is between about 1000 seem.里晴约0.1 _ to 30 1310967 w· ^ ^ I -- Year 'Monthly's repairs ££ for cover i&quot; 25. If the application = scope of the 23rd method of Ru metal ^ substrate, where the CO gas A flow rate is between ρ and 丨 between about 1 seem and about 100 seem. J 26. A method of depositing Ru metal on a patterned substrate as claimed in claim 23, wherein the processing gas forming step further comprises: passing a carrier gas over or through the rU3(CO)12 precursor 3 things. 27. A method of depositing a RU metal on a substrate as claimed in claim 26, wherein the carrier gas comprises a rare gas. 8. Oralization 28. A method of depositing a Ru metal on a substrate, as in claim 26, wherein the flow rate of one of the carrier gases is between about sc1 sccm and 1000 seem. 29. A method of depositing RU metal on a patterned substrate as claimed in claim 23 wherein the heating step comprises: maintaining the RuKCO) precursor at a temperature of between about 4 Torr.匸 150oC. 30. A method of depositing Ru metal on a patterned substrate as in claim 23, wherein the heating step comprises: maintaining the Ru3(CO)i2 precursor at a temperature between about 60 ° C and about Between 90 ° C. w. The method of depositing Ru metal on a patterned substrate according to claim 23, further comprising: maintaining the substrate at a temperature between about 50 QC and about during the step of exposing the patterned substrate 500 ° C. 31 1310967 Amendment Replacement Page Substrate ^^ Item 23 (4) Metal deposition in patterning a temperature During the exposure step of the patterned substrate, the substrate is maintained at a temperature between about 300 ° C and about 400 ° C. 33. The method of depositing Ru metal on a patterned substrate as in claim 23, further comprising: maintaining the processing chamber at a pressure of between about 0.1 mTorr during the step of exposing the patterned substrate to About 2 〇〇 mTorr. 34. The method of depositing Ru metal on a patterned substrate as in claim 23, further comprising: • maintaining the processing chamber at a pressure of between about 1 mTorr during the patterning substrate exposure step To about 1〇〇mT〇rr. 35. The method of depositing Ru metal on a patterned substrate according to claim 23, further comprising: φ maintaining the processing chamber at a pressure of about 2 mTorr during the patterning substrate exposure step Up to about 50 mTorr. 36. The method of depositing Ru metal on a patterned substrate according to claim 23, wherein the diluent gas addition step comprises: adding the diluent gas to the processing gas in the vapor distribution plenum; The diluted gas flows through the vapor distribution plate to the treatment zone. 37. Depositing Ru metal in the patterning according to item 23 of the patent application scope 1310967 ▼ month The method of the substrate, wherein the diluent gas addition step comprises: flowing the treatment gas through the vapor to add the diluent gas to the processing gas. In the method of claim 23, the method of depositing Ru metal on the patterned substrate, wherein the diluent gas addition step comprises: adding the diluent gas to the vapor distribution plate (10) The process gas. 39. A method of depositing Ru metal on a patterned soil as claimed in the scope of claim 帛a, wherein the diluent gas comprises a rare gas. 40. A method of depositing Ru metal on a patterned substrate as claimed in the scope of the patent, wherein the diluent gas further comprises a reducing gas. 41. A method of depositing Ru metal on a patterned substrate as claimed in the patent application, wherein the reducing gas comprises: H2, - containing gas, gas containing gas, or gas containing gas Combination of species or more. 42. The method of depositing Ru metal on a patterned substrate according to claim </ RTI> wherein the patterned substrate further comprises: a barrier layer formed on the sized substrate, the Ru metal Accumulate on it. 43. A method of depositing Ru metal on a patterned substrate as claimed in claim g, wherein the barrier layer comprises: a layer comprising a layer or a layer comprising a tungsten layer onto which the metal layer is deposited . 44. A method of depositing Ru metal on a patterned 1310967 τ. Danish modified replacement page substrate, as claimed in claim 23, wherein the process gas forming step = the Ru3(CO)12 precursor vapor relative to the C〇 gas 匕 to control the decomposition rate of the Ru3(CO)12 precursor on the patterned substrate, 45. As in the scope of claim 23, the method 丨, the type of substrate is more: in the figure The thermal vapor deposition process is characterized in the dynamic limit H recording ® Schönau. 46. A deposition system comprising: a processing chamber having a vapor distribution system; a substrate support located in the processing chamber, and (4) supporting and heating-substrate; and a material (10) coupled to the gas and system? Using: forming a wire-containing metal precursor to vaporize the vapor distribution gas and using the process gas to pass to a dilution gas source, the body is connected to the processing chamber, and the body is added to the processing chamber Diluting, liquefying the gas; and carcass to form a diluted layer deposited on the iiif material - thermochemical __ process to transfer a metal to the deposition system of claim 46, wherein the precursor is formed; =: Γ heating, base metal precursor with vapor = 0 gas source 'to make the co gas and the metal precursor 34 佗 10967 — — — 在 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 Wherein the L-c〇^ integrated source is used to mix the CO gas with the carbonyl metal precursor vapor from downstream of the metal carbonyl precursor.沉积 49. The deposition system of claim 47, wherein the c〇 gas source is used to cause the CO gas and the carbonyl metal precursor by flowing the CO gas over or through the base metal drives The vapor is mixed. 50. The deposition system of claim 47, wherein the transfer system is configured to flow the co gas at a gas flow rate between about 〇 i and about 1000 seem. S&lt;Xm 5L is a deposition system of claim 47, the delivery system is for causing the CO gas to flow between (1) a body of about 100 seem. 'discern to 52. The deposition system of claim 46, the delivery system is more dependent on the flow surface or the precursor drive 53. The deposition delivery system of claim 52 is used to make The carrier gas flows between a gas flow rate; ' ^ υ '1 seem to about 54. The sinking seat of claim 46 is used to heat the substrate to a substrate temperature first among the substrate branches. "Sentence 50 ° C to about 5 ° C. 55. As claimed in the scope of claim 46, 35 1310967 replacement page is used to maintain the processing chamber at a pressure of between about 0.1 mTorr to about 200 56. The deposition system of claim 46, wherein the diluent gas source is for adding the diluent gas to the process gas in a vapor distribution plenum of the vapor distribution system. The deposition system of item 46, wherein the diluent gas source is for adding the diluent gas to the processing gas between the vapor distribution system and the substrate. 58. The deposition system of claim 46, Wherein the diluent gas source is used to add the diluent gas to the processing gas in a vapor distribution plate of the vapor distribution system. Η*1, schema: