TW200822191A - Precursors and hardware for CVD and ALD - Google Patents

Abstract

The present invention generally comprises an apparatus for depositing high k dielectric or metal gate materials in which toxic, flammable, or pyrophoric precursors may be used. Exhaust conduits may be placed on the liquid precursor or solid precursor delivery cabinet, the gas panel, and the water vapor generator area. The exhaust conduits permit a technician to access the apparatus without undue exposure to toxic, pyrophoric, or flammable gases that may collect within the liquid deliver cabinet, gas panel, and water vapor generator area.

Description

200822191 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION [0001] Embodiments of the present invention generally relate to the deposition of high dielectric properties by atomic layer deposition (ALD) or chemical vapor deposition (CVD) & And • Metal gate materials are precursors and hardware. [Prior Art] 平面 In the field of semiconductor manufacturing, flat panel display processes or other electronic component processes and vapor deposition processes have played an important role in depositing materials on substrates. As the geometry of electronic components continues to shrink and the density of components continues to increase, the size and aspect ratio of the features become more advanced, such as the feature size of 0. 07 nm and the depth of 1 〇 or greater. Width ratio. Therefore, the conformal deposition of materials to form these components has become increasingly important. ”

While conventional CVD has proven successful for component geometries and aspect ratios as low as 0.55 nm, more advanced component geometries require C/'s deposition techniques. One technique that has received attention is ALD. During the ALD • process, reactant gases are sequentially introduced into a process chamber containing the substrate. Typically, the first reactant is pulsed into the process chamber and adsorbed onto the surface of the substrate. The second reactant is pulsed into the process chamber to & reacts with the first reactant to form a deposition material. Typically, a purge step is performed between the transport of each reactant gas. The purification step can be a continuous purification using a carrier gas or a pulsed purification between reactant gas delivery. 5 200822191 The formation of high-k dielectric materials by oxidizing metal and hafnium precursors during the ALD process is well known in the art. Ozone, atomic oxygen, and water are common oxide or oxidation sources used in ALD processes. During the deposition process, low process temperatures can be advantageously maintained due to the free radical state of ozone and atomic oxygen while forming a dielectric material. If you can control the process, you can also use two-temperature, south-oxidized electric loading. Therefore, this art requires a device that can perform deposition of high-k dielectric or metal gate materials that can operate in high oxidation plasma environments at elevated temperatures. SUMMARY OF THE INVENTION The present invention generally comprises an apparatus for depositing a high-k dielectric or metal gate material using a toxic, flammable or ignited precursor. The discharge conduit can be disposed in the liquid precursor or solid precursor delivery cabinet, the gas faceplate, and the water vapor generator zone. The exhaust conduit allows the technician to enter the device without unduly exposed to toxic, igniting or flammable gases collected in the liquid transfer cabinet, gas faceplate and water vapor generator area. Inside. In one embodiment, the present invention discloses a vapor deposition apparatus. The apparatus comprises: a liquid precursor or solid precursor delivery cabinet having a discharge line coupled thereto; a gas faceplate having a discharge line coupled thereto; a water vapor generator system having a discharge line Coupled with it; and one or more sources of toxic, flammable or ignited precursors. In another embodiment, the present invention discloses a vapor deposition method. The method of 2008 200821191 comprises: introducing at least one precursor to a device having a liquid precursor or solid precursor delivery cabinet, a gas faceplate and a water vapor generator system, the precursor being selected from the group consisting of toxic precursors a group of flammable precursors and igniting precursors; expelling precursor gases from the liquid delivery cabinet, • the gas faceplate or at least one of the water vapor generator systems; and _ depositing a layer on a substrate. f. [Embodiment] The present invention generally comprises an apparatus for depositing a high-k dielectric material or a metal gate material in which a toxic, flammable or ignited precursor is used. A discharge conduit can be provided for the liquid precursor or solid precursor to transport the gas faceplate to the water vapor generator zone. The venting conduit allows the technician to operate the equipment without excessive exposure to toxic, igniting or flammable gases collected in the liquid precursor or solid precursor delivery cabinet, gas faceplate, and water vapor generator zones. Exemplary high-k" dielectric materials that can be deposited include Hf〇2, HfSiO, ΡΓ2Ο3, La2〇5, Zr〇2, 1/ZrS10, Al2〇3, LaAlO, Ta205, Ta05, A105, and Ti05. ^ Demonstrated exemplary metal gate material includes TaN, TiN, TaSiN,

Ru, Pt, TiAIN and HfN. Other film systems that can also be deposited include polycrystalline spine, SiN and HT0. This equipment can be an ALD reactor or a CVD reactor. 1 is a cross-sectional view showing a process chamber 100 in which integrated circuit fabrication can be performed in accordance with an embodiment of the present invention. The process chamber 100 contains a thermally insulating material to operate at high temperatures (e.g., < 800 ° C). The process chamber 100 may include a liner made of a thermally insulating material such as fused quartz, sapphire, pyrolyzed boron nitrite (PBN) material, ceramic, a derivative thereof, or a composition thereof. The process chamber to 100 generally houses a substrate support carrier 164 for supporting the substrate 166. The substrate support carrier 164 can be rotated within the process chamber 100 and moved vertically. The substrate support carrier 164 can include a heating member to control the temperature of the substrate 丨6 6 thereon. The cover portion 172 is located on the cover 12 of the process chamber 1 and includes a plurality of gas inlets 114. The cover portion 172 may also include a adapter 168 for use in a microwave device or a remote plasma device during a plasma process such as a PE-ALD process, a pre-clean process, or a post-treatment process such as a nitridation process. . Alternatively, the cover portion 172 does not have a adapter ^8. The gas face plate 106 is connected to the process chamber 1 through the cover portion 172. The gas face plate 106 includes at least one and up to about ten component sets of gas inlets 114 conduits 108, 110, valves 112, and at least one precursor source. As shown in Fig. 1, the gas panel 1〇6 comprises two component groups including a gas inlet 11 4, a conduit system 1 1 〇, a valve u 2, and a precursor source. Valve i J 2 can be a fast switching valve that can pulse inject reactants or oxides. Precursors can be provided in the reservoir to ensure adequate precursors. In an alternative embodiment, the catheter system 1 〇 8, 110 may further comprise a progressively expanding gas conduit, thereby forming a nozzle at the end that is also in communication with the gas inlet 1 14 . Nozzles or end systems for use in some embodiments of the present invention are further described in commonly assigned U.S. Patent Application Serial No. 2005/0252449 A1, which is incorporated herein in

reference. The gas conduit geometry avoids large temperature drops by providing a passing gas to the device that progressively expands through the progressively tapered flow channel. In one embodiment, the flow channel transitions from a delivery gas line having an inner diameter of from about 3 mm to about 15 mm to a distance of from about 1 mm to about 20 mm along a distance of from about 30 mm to about 100 mm. A larger diameter gas inlet 11 4 . The increasing diameter of the flow channels allows the expanded gas to be approximately balanced and avoids rapid heat loss to maintain a substantially constant temperature. The expanded gas conduit may comprise one or more tapered inner surfaces, such as tapered straight surfaces, concave surfaces, convex surfaces, derivatives thereof, or combinations thereof, or may comprise one or more tapered inner surfaces Multiple sections (eg, partially tapered and partially untaped). The conduit system 108, 110 includes one or more conduits and conduits that connect the gas inlet 114, the valve 112, and the gas faceplate 106. Valve 112 can include a valve and a valve seat assembly having a diaphragm and a valve seat. The pneumatically actuated valve provides a pulse of gas as low as approximately 0·0 2 0 seconds. The electrically actuated valve can provide a pulse of gas for periods as low as about 0.005 seconds. In general, the pneumatic and electrically actuated valves can provide gas pulses for periods up to about 3 seconds. While higher periods of gas pulses are possible, a typical ALD process uses an ALD valve that produces a gas pulse while simultaneously opening a gap of about 5 seconds or less. In an embodiment, the valve can be opened for an interval of about 3 seconds or less. In yet another embodiment, the valve can be opened for an interval of about 2 seconds or less. In one embodiment, the ALD valve is pulsed at intervals of from about 0.005 seconds to about 3 seconds. In another embodiment, the valve train is pulsed at intervals of from about 0.002 seconds to about 2 seconds. In yet another embodiment, the valve train is pulsed at intervals of from about 0.05 seconds to about 9 200822191 1 second. Typically, an electrically actuated valve requires the use of a driver between the valve and the programmable logic controller. The process chamber including the valve i丨2, the precursor source, the vacuum system 150, the substrate support carrier 164, the water vapor generator (WVG) system i〇4, and the gas panel 1〇6 can be There is a control unit (not shown), such as a programmed personal computer, workstation computer, etc., to control the processing conditions described herein. As shown in Figure 3, the WVG system 1〇6 can be positioned below the chamber. f. Gas panel 110 may provide a precursor source, a purge gas source, and/or a carrier gas source for use during the deposition process. The precursor source can include more than one chemical precursor (e.g., ruthenium precursor and ruthenium precursor) and can include a carrier gas. The precursor source includes an ampoule, a bubbler, a tank, a container, and a cartridge. In addition, the precursor source includes a wvo system 104' coupled to source 1〇2 and in fluid communication with gas panel ι6. The purge gas source and/or the carrier gas source, typically a tank, vessel, cartridge, or internal piping supply system, may provide nitrogen, argon, helium, hydrogen, forming gas, or a combination thereof to the gas faceplate 10 6. • The gas inlet 114 can be disposed within the shroud 1 72 along the length of the dilation channel Π6. Without wishing to be bound by theory, the gas flowing in from the gas inlet port 4 and flowing through the expansion channel 1 16 forms a circular stream. While the correct flow pattern through the expansion passage 116 is unknown, it is believed that the circular flow travels through the expansion passage 116 in a flow pattern such as a thirst, a spiral, a spiral flow or a derivative thereof. A circular stream can be provided in a processing region between the funnel liner 122 and the substrate support 1 64. In one aspect, the eddy current helps to efficiently purify the treated area due to the sweeping action of the circular flow on the inner surface of the expansion channel 161. In addition, the circular gas stream provides consistent and conformal gas delivery on the surface of the substrate 166. Figure 1 illustrates a thermally insulating liner that can be used in the process chamber 1 and other process chambers during the deposition process described herein. The expansion channel 1 16 can be formed in the hood portion 1 72 and between the hopper liners 1 22 . A thermal insulator 1 70 is disposed around the cover portion 1 72. By aligning the projecting surface 124 of the retaining ring liner 128 with the retaining surface of the hopper liner 122 by the retaining ring liner 128, the hopper liner 122 can be secured against the underside of the lid 120. The retaining ring lining 1 28 can be attached to the underside of the cover 120 by fasteners 1 2 6 (eg, fitting fittings, bolts, screws, or tips). In one example, the fixture 1 26 is a fitting that is inserted and secured into the groove of the retaining ring liner 1 28 . The funnel lining 122 can also include a plurality of loosely embedded tips 181 to provide the free expansion of the funnel lining 1 22 during the heating process. In one embodiment, after the thermal swell of the hopper liner 1 22, the funnel lining 1 22 becomes aligned and aligned toward the substrate 1 64. Alternatively, the funnel lining 1 22 and the retaining ring lining 1 28 may be formed as a single piece. The process chamber 100 can further include an upper process liner 132 and a lower process liner 162. The lower process liner 162 is disposed on the bottom surface and the upper process liner 132 is disposed on the lower process liner 162 and along the wall surface 140 of the chamber body 148. A slit valve liner 136 is positioned to protrude through the upper process liner 132 and into the process area. The lining (including the funnel lining 122, the retaining ring lining 128, the upper process lining 132, the lower process 11 200822191 lining 1 62 and the slit valve lining 1 3 6 ) is a thermally insulating material such as a painful $ sapphire, sapphire, PBN Materials, ceramics, tantalum carbide, aluminum ruthenium 6, derivatives thereof, or combinations thereof. In one embodiment, the liner is j, μ ° steel or sinter or graphite 'and is coated with a thermal insulator as described above* by lining the coated P BN, water vapor does not adhere To the bare lining's bare lining • This does not cause the precursor to react and deposit on the lining surface. Usually ' a A is released stress to avoid the initiation of the deposition process described here,

.〇 〇 0 °C Γ, causing failure to the thermal cycle during cycling. The lining can withstand temperatures of about t 1 〇 0 〇 °^ or higher. In another embodiment, the liner can withstand temperatures of about 12 Torr or higher. In yet another embodiment, the liner can tolerate temperatures of about °C or higher. In addition, the lining can be flam polished to achieve a surface finish of about 2 microinch (about 0.051 nm) or less. The polished smooth surface provides a smooth surface so that the process reactant delivers little or no turbulence, and the polished surface reduces nucleation on the liner (which may not be desirable on it) Promote film growth). Furthermore, flame polishing removes surface defects such as potholes and cracks to reduce the nucleation of defects caused by thermal stress. • The purge line 13 is a chamber backside purge line that is disposed from the bottom of the chamber body 148 to the chamber lid 120 and the funnel liner 122. The purge line 130 is positioned such that purge gas flows between the wall surface 14 〇 and the upper/lower process liners 132, 162 and into the process area. The source of purge gas can be connected to purge line 130 via inlet 146. The purge gas flowing through the purge line 130 avoids the wall surface 140 from contaminants and excessive heat emanating from the process area. Contaminants include precursors or reaction products that may bypass the process linings 132, 162 of the upper / 12 200822191 and deposit heat on the wall surface ι4 〇 process area may escape the upper/lower process lining and be absorbed into the process body 148. However, state-of-the-art purified steroid bundles transport contaminants and heat back into the process area. Disposed on the outside of the chamber body 148 to prevent heat from the process-process liner 132 and the lower process liner ι62 may be included to accommodate a plurality of substrate lifts during the movement of the substrate 166. The process liner 132 and the lower process liner 162 may be disposed. Align with the lifting tip hole. The upper process lining 1 3 2 further includes a transfer joint 154 and a slit valve 埠 134 to accommodate the narrow drive outlet 154 disposed to pass through the chamber body ι 48 so that the process area is in fluid communication with the vacuum system 1 5 〇 The slit valve liner 136 is moved into and out of the process chamber 1 . It can also protrude through the heat blocking plate 142. By using a clogging gap 丨 56, the clogging gap 156 can be controlled to form a space between the tops of the bottom pedestal 164 of the hopper liner 122. The clogging gap 156 can be reduced by the process conditions and the desired cylinder suction efficiency gap 156 by lowering the substrate support carrier 164 to support the carrier 丨 64. The film thickness and uniformity during the deposition process described can be varied by changing the blockage to change the enthalpy from the lower portion of the process chamber 100 to the sigma of the expansion. In order to increase the efficiency of gas discharge from the chamber 100. In addition, the purge gas clogging plate 142 from 132, 162, and _ 130 is lost in the set area. Upper lift holes, tips (not shown). The upper part is in the process chamber and the vacuum is 埠160, and the I valve lining is 163. Row with vacuum 埠 1 60,. The substrate 1 6 6 is pumped through the slit valve lining 1 3 6 . The edge and substrate support are loaded as a surrounding gap and the rate is changed. Blocking 増, or by pumping the 距 升 升 升 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 埠 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮 涡轮Or in-line. The turbomolecular pump 152 can be activated or continuously operated as needed to remove oxide from the chamber 100 and avoid mixing of the oxide with the precursor. If the oxide is mixed with the precursor The reaction will occur and a micro-particle 0' chamber cover 1 2 can be generated. The plurality of heater rods 1 74 can be maintained at a constant temperature, wherein the heater rods 174 are coupled to the cover. The chamber body 148 ( It can also be heated by a plurality of heater rods 176. The heater rods 174, 176 can be electrically charged or can have a heating fluid flowing therein. Alternatively, the heater rods 174, 176 can be replaced with a heat exchanger. The heat exchanger can cool the lid 120 and the chamber body 148. Precursor condensation can be reduced by maintaining the lid 12 and the chamber body 1 48 at a constant temperature. The substrate carrier 1 64 can be Heating or cooling. The substrate carrier 64 can be used by The fluid flowing through the heat exchanger is cooled. Alternatively, the substrate carrier i 64 can be heated. The substrate carrier 64 can have a dual block heater so that the substrate 16 6 can be controlled to a temperature of about 15 〇 〇 and about 800 ° C. In the embodiment of D, the temperature can be controlled at about 20 〇. Control of the various zones to enhance the temperature uniformity from the center to the edge of the substrate 166. The ALD process can be performed in the process chamber at a pressure range from about 1 Torr to about 1 Torr. In one embodiment, the pressure It can be from about 1 Torr to about 2 Torr. In yet another embodiment, the pressure can be from about 1 Torr to about 1 Torr. The pressure in the process chamber is less than the pressure in the reservoir providing the precursor. The temperature can be maintained from about 70 〇c to about 100 (rc. In one embodiment, this range 14 200822191 can be about loot: to about 650. (In yet another embodiment, this range can be about 250°) C to about 50 〇. (: When forming a metal gate material, a ruthenium-containing compound can be introduced, for example a pulse of pentadimethy lamino-tantalum (PDM AT; • Ta(NMe2)5). It is provided by a carrier gas to provide a button-containing compound, wherein the carrier gas system includes It is not limited to helium, argon, nitrogen, hydrogen, and combinations thereof. A pulse of a nitrogen-containing compound (such as ammonia) can be introduced. F is also used to use a carrier gas to facilitate the transport of nitrogen-containing compounds. The gas (e.g., argon) can continuously provide a flow of the purge gas as a purge gas between the pulse of the group-containing compound and the nitrogen-containing compound, and as a pulse during the pulse of the ruthenium-containing compound and the nitrogen-containing compound. Carrier gas. In one aspect, the purge gas is delivered via two gas conduits rather than via a gas conduit. In one aspect, a reactant gas can be delivered via a gas conduit because the flow of the reactant gas (eg, the neon-containing compound and the nitrogen-containing compound) is less important than the uniformity of the purge gas. Because of the self-destruction of the reactants on the surface of the substrate structure, I limit the absorption process. In other embodiments, the purge gas is provided in a pulsed manner. In other embodiments, more or less than two gas streams are provided to provide purge gas. In other embodiments, more than a single gas stream (i.e., two or more gas streams) is provided to provide a ruthenium containing compound. In other embodiments, more than a single gas stream (i.e., two or more gas streams) is provided to provide a nitrogen containing compound. Examples of other ruthenium containing compounds include, but are not limited to, organometallic precursors or derivatives thereof, such as penta(ethyl decylamine) knobs 15 200822191 ( pentaethy lmethy lamino_tantalum, PEM AT .

Ta[N(C2H5CH3)2]5), penta(diethylamine) group (pentadiethylamino-tantalum, PDEAT; Ta(NEt2)5), and any of PEM AT, PD EAT or P DM AT Things. Other ruthenium containing compounds include, but are not limited to, TBTDET (Ta(NEt2)3NC4H9 or Ci6H39N4Ta), and group halides (such as TaXs, where X is fluorine (F), bromine (Br) or chlorine (C1)), and / Or a derivative thereof.

When a high-k dielectric layer is formed, a stack of precursors is introduced into the process chamber at a rate of from about 5 seem to about 200 seem. The ruthenium precursor can be introduced with a carrier gas (e.g., nitrogen) at a total flow rate of from about 50 s c c m to about 10 〇 〇 s c c m . The ruthenium precursor is pulsed into the process chamber at a rate of from about 0.1 second to about 10 seconds (depending on the particular process conditions, the ruthenium precursor, or the desired composition of the deposited ruthenium containing material). In one embodiment, the ruthenium precursor is pulsed into the process chamber at a rate of from about 1 second to about 5 seconds (e.g., about 3 seconds). In another embodiment, the ruthenium precursor is pulsed into the process chamber at a rate of from about 丨 丨 丨 to about 1 sec (e.g., about 0.5 sec). In one example, the hafnium precursor is hafnium tetrachloride (HfCU). In another example, the hydrazine is a tetrakis(dialkylamine) compound such as tetrakis(diethylamine) ruthenium ((Et2N)4Hf or TDEAH). As shown in Fig. 2A, the ruthenium or osmium precursor can be dispensed into the process chamber 2〇2 by introducing a carrier gas through a container 206 containing a ruthenium or osmium precursor. The valley phase 206 can include a container, a bubbler, or other container for containing or dispensing a chemical precursor. A suitable container (eg PROE-VAPTM) is from Advanced 16 200822191 in Danbury, Connecticut, USA.

Purchased by Technology Materials. The tank 2〇6 is in fluid communication with the process chamber 202 via conduit 2i8. The conduit 218 can be a wheel tube, tube, wire, hose, or other conduit known in the art. In addition, the tanks 2〇6 are spaced apart from the process chamber 202 by a distance 220. The distance 220 is typically less than about 2 meters. In an embodiment, the distance #220 can be less than about 125 meters. In yet another embodiment, the distance can be about 0.7 meters or less. The distance 220 ' can be shortened to maintain a consistent 姶 or 钽 precursor flow. Furthermore, although the conduit 21 8 may be straight (four) curved, m18 is preferably straight or has as few bend points as possible. The conduit 2U can be wound by a heating belt to maintain a predetermined temperature. The temperature of the tank 206 is maintained at a temperature of, for example, about 2 Torr: to about 3 ° C depending on the 铪 or button precursor therein. In one embodiment, the tank 206 holds four gasification crucibles at about 150. 〇 to a temperature of about 2〇〇t:. It should be understood that although zirconium is exemplarily used as a high-k dielectric material, zirconium can also be used. In an embodiment, the container 206 can be a component of a liquid delivery system containing a syringe valve system 21A. The liquid delivery system is housed within a gas panel 208. The syringe valve system 21 is coupled to the tank 206 and the process chamber 202 by a conduit 218. A carrier gas source (not shown) can be coupled to the injector valve system 210. A tank 206 containing a liquid precursor (e.g., Tdeah, tdmah, TDMAS, or TrU-DMAS) can be pressurized to deliver a liquid precursor to the syringe valve system 210. The tank 2 〇 6 containing the liquid precursor can be pressurized, from about BSkPa (about 20 psi) to about 4 MPa (about 6 〇).

The pressure of PsU can be heated to a temperature of about 100 t or less. In the embodiment, this temperature system is about caught, about (10). The syringe crucible system 17 200822191 2 1 0 combines the liquid precursor with the carrier gas to form a precursor vapor that is injected into the process chamber 02. The carrier gas can include nitrogen, argon, helium, hydrogen, or combinations thereof, and the carrier gas can be preheated to a temperature of from about 85 °C to about 150 °C. A suitable syringe valve is commercially available from Ho riba-Stec, Tokyo, Japan.

The oxidizing gas is introduced into the process chamber 202 at a flow rate of from about 0.05 seem to about 1 000 seem. In one embodiment, the flow rate is from about 0.5 seem to about 100 seem. The oxidizing gas is pulsed into the process chamber 2 0 2 at a rate of from about 0.05 seconds to about 10 seconds. In one embodiment, this range is from about 0.08 seconds to about 3 seconds. In yet another embodiment, the range is from about 1 second to about 2 seconds. In one embodiment, the oxidizing gas system is at a rate of from about 1 Torr to about 5 seconds (e.g., about 1.7 seconds). Pulsed introduction. In another embodiment, the oxidizing gas system is pulsed in at a rate of from about 0. 1 second to about 3 seconds (e.g., about 0.5 seconds). Oxidizing gas may be generated by WVG system 204, which is in fluid communication with process chamber 202 via conduit 214. Connector fittings 212, 216 can be used to connect conduit 214 to WVG system 204 or to process chamber 202. Suitable fittings include UPG fittings, which are commercially available from Fujikin of America, USA. The conduit 214 can be in fluid communication with the process chamber 202 via an ALD valve assembly. The conduit 214 can be a tube, tube, wire or hose made of metal (e.g., stainless steel or aluminum), rubber or plastic (e.g., PTFE). In one example, a tube formed of stainless steel 316L is used as the conduit 214. The WVG system 204 produces ultra-high purity water vapor by a catalytic reaction of an oxygen source gas (e.g., helium 2) with a hydrogen source gas (e.g., H2) at a low temperature (e.g., < 500 18 200822191 °c). Each of the hydrogen and oxygen source gases flows into the W V G system 204 at a flow rate of from about 5 s c c m to about 200 s c c m . In one embodiment, the flow rate can be from about 10 seem to about 100 seem. The flow rates of the oxygen and hydrogen source gases can be independently adjusted so that there is an oxygen or oxygen source gas in the effluent of the oxidizing gas and no hydrogen or hydrogen source gas is present. The oxygen source gas which can be used to generate an oxidizing gas containing water vapor can include oxygen, atomic oxygen, ozone, nitrous oxide, nitrogen monoxide, nitrogen dioxide, dinitrogen pentoxide, hydrogen peroxide, derivatives thereof, or Its composition. The hydrogen source gas which can be used to generate an oxidizing gas containing water vapor can include hydrogen, atomic hydrogen, produced gas (N2/H2), ammonia, hydrocarbons (such as CH4), alcohols (such as CH3OH), derivatives thereof, Or a composition thereof. A carrier gas may be co-flowed with an oxygen source gas or a hydrogen source gas and may include nitrogen, helium, argon, or combinations thereof. The oxygen source gas is oxygen or nitrous oxide, and the hydrogen source gas is hydrogen or a generating gas (e.g., 5% by volume of hydrogen in nitrogen). The hydrogen source gas and the oxygen source gas can be diluted with a carrier gas to sensitively control the water vapor in the oxidizing gas during the deposition process. In one embodiment, a slower water vapor flow rate (about < 10 s c c m water vapor) is desired to complete the chemical reaction during the ALD process to form a germanium containing material or other dielectric material. The slower water vapor flow rate is the dilution of the water vapor concentration in the oxidizing gas. The concentration of the diluted water vapor can oxidize the precursor adsorbed on the surface of the substrate. Therefore, a slower water vapor flow rate reduces the purification time to increase manufacturing capacity. In addition, the slower water vapor flow rate reduces particulate contaminant formation by avoiding undesirable co-reactions. When in manufacturing 19 200822191

When there is a water vapor beam with a flow rate of about 0 · 5 s c c m , a mass flow controller (MFC) can be used to control the hydrogen source gas to have a flow rate of about 0.5 s c c m . However, most MF systems are unable to provide consistent flow rates at such flow rates. Therefore, a diluted hydrogen source gas (e.g., generated gas) can be used in the WV G system to achieve a slower water vapor flow rate. In one example, a hydrogen source gas system having a flow rate of about 10 seem and containing 5% hydrogen generating gas delivers water vapor from the W V G system at a flow rate of about 0.5 s c c m . In an alternative embodiment, when forming a bell-containing material or other dielectric material, a faster water vapor flow rate (about > 10 sccm water vapor) is desired to complete the chemical reaction during the ALD process. . For example, about 100 seem of hydrogen transports about 10 s c c m of water vapor. The gas produced can be selected to have a hydrogen concentration of from about 1% to about 95% by volume of the carrier gas (e.g., argon or nitrogen). In one aspect, the hydrogen concentration of the generating gas is from about 1% to about 30% by volume of the carrier gas. In one embodiment, the gas system is formed from about 2% to about 20%. In yet another embodiment, the gas system is formed from about 3% to about 10%. For example, the generated gas may comprise about 5% hydrogen and about 915 nitrogen. In another aspect, the hydrogen concentration of the generating gas is from about 30% to about 95% by volume of the carrier gas. . In another embodiment, the hydrogen concentration is from about 40% to about 90%. In yet another embodiment, the hydrogen concentration is from about 50% to about 85%. For example, the generated gas may comprise about 80% hydrogen and about 20% nitrogen. In one example, the WVG system receives a hydrogen source gas containing 5% hydrogen (95% nitrogen) at a flow rate of about 10 seem and an oxygen source gas (e.g., oxygen) at a flow rate of about 10 sccm to form a flow rate of about 0.5 sccm. Oxidizing gas containing water vapor and oxygen at a flow rate of about 9.8. In another example, the WVG system 20 200822191 receives an oxygen source gas having a flow rate of about 2 0 sccm of a hydrogen source gas containing 5% hydrogen generating gas to form an oxidizing gas of about 1 seem flow rate gas and about 9 sccm. Oxygen at the flow rate. In another WVG system, a hydrogen-containing source of hydrogen gas having a flow rate of about 20 scem is passed to an oxygen source gas of about 1 〇 S c c m flow rate to form an oxidizing gas of about 10 s c c m water vapor and oxygen at a flow rate of about 9.8 sccm. In the example, nitrous oxide, which is one of the oxygen source gases, can be used with the hydrogen source to form water vapor during the ALD process. In general, 2 C, nitrous oxide replaces each molar equivalent of oxygen. The WVG system comprises a catalyst, such as a catalyst or a catalyst cartridge in which an oxidizing gas containing water vapor is produced by a catalytic reaction between oxygen sources. The w V G system is different from a pyrogenic generator, which typically produces water vapor at temperatures in excess of temperature. The WVG system containing the catalyst produces water vapor at a low temperature of from 1 t: to about 500 °C. In one implementation you can be about 350 ° C or lower. The catalyst may be contained in a catalyst reactor. The agent may include a metal or an alloy such as palladium, platinum, nickel, iron, rhodium, an alloy thereof, or a combination thereof. Ultra high purity water is desirable for the process of the invention. In one embodiment, to avoid unreacted negatives, the oxygen source gas system is allowed to flow through the WVG system for a long time, and the hydrogen source gas is allowed to enter the reactor for 5 seconds. The catalytic reaction between oxygen and (e.g., hydrogen and oxygen) produces water vapor. The flow of the hydrogen source gas can precisely control the concentration of oxygen and hydrogen in the formed aqueous cold gas. The water vapor may comprise a hydrogen source gas body and about the aqueous steaming example, the gas and the flow rate of the other embodiments together with the molar equivalent, the reaction of the agent from the hydrogen source and the heat generator 1000 ° C, in about 100 | In this temperature, the catalytic chrome, ruthenium, and ALD system 4 flow downstream for 5 seconds. The hydrogen source gas regulates the oxidation of oxygen and gas [, the oxygen source gas 21 200822191 body, or a combination thereof, a suitable WVG system", such as WVG and/or the United States sold by Fujikinof America, Santa Clara, California, USA. Catalyst Stem Generator System (CSGS), sold by Ultra Clean Technology, Menlo Park, California. Figure 2B depicts the configuration of the WVG system 204. Hydrogen source 244, oxygen source 248, and carrier gas source 246 may be coupled to WVG system 204 by conduit system 242. The conduit system 242 includes a plurality of conduits and a plurality of valves that can independently fluidly communicate gas from the hydrogen source 244, the oxygen source 248, and/or the carrier gas source 246 via the gas input port 240 to the gas filter 2368. In the catalyst reactor 2 3 6 . In addition, conduit system 242 includes a plurality of conduits and a plurality of valves that can bypass gas from hydrogen source 244 and oxygen source 248 independently of catalyst reactor 236 at junction 234. Therefore, an additional hydrogen source gas and/or oxygen source gas can bypass the catalyst reactor 236 and combine with water vapor to form an oxidizing gas containing oxygen and helium. Gas sensor 232 and gas eliminator 230 may be coupled to conduit system 242 downstream of catalyst reactor 236. The gas sensor 2 3 2 is used to determine the composition of the oxidizing gas, including the oxygen and nitrogen fish water concentrations. The oxidizing gas can pass through the gas filter 230 before exiting the WVG system 204. The pulse of the purge gas is introduced at a flow rate of from about 2 slm to about 22 sim. In an embodiment, the purge gas can be argon or nitrogen. In another embodiment, the flow rate can be about 10 slm. Each process cycle lasts from about 1 second to about 20 seconds. In one example, the process cycle lasts about 1 second. In another example, the process cycle lasts for about 2 seconds. Longer treatment steps lasting about ι〇 seconds will deposit a good film containing ruthenium, but reduce productivity. The flow rate of the purge gas and the duration of the process cycle are obtained through experiments. In one example, a 300 mm wafer requires approximately twice the flow rate for a 200 mm wafer system of the same duration to maintain comparable throughput. In one embodiment, hydrogen can be used as a carrier gas, a purge gas, and/or a reactant gas to reduce halogen contamination of the deposited material. Precursors containing elemental atoms (e.g., HfCl4, SiCl4, and Si2Cl6) tend to contaminate the deposited dielectric material. Hydrogen is a reducing agent and can produce hydrogenated hydrogen (e.g., HCl) as a volatile and removable by-product. Therefore, when hydrogen is combined with a precursor compound (e.g., helium, neon, or oxygen precursor), hydrogen can act as a carrier gas or reactant gas, and can include another carrier gas (e.g., argon or nitrogen). In one example, a water/hydrogen mixture at a temperature of from about 10 ° C to about 500 ° C can be used to reduce the concentration of halogen and increase the oxygen concentration of the deposited material. In one example, the water/hydrogen mixture can be produced by injecting an excess of hydrogen source gas into the WVG system to form hydrogen-rich hydrogen. In one embodiment, the ruthenium precursor can be dispensed into the process chamber 202 by introducing a carrier gas through the containment vessel 206 containing the ruthenium precursor, as shown in Figure 2A. The temperature of the tank 206 can be maintained, for example, at a temperature of from about 20 ° C to about 300 ° C, depending on the ruthenium precursor therein. In one embodiment, the tank 206 is comprised of HfCl4 at a temperature of from about 150 °C to about 200 °C. A tank 206 containing a liquid precursor (e.g., TDEAH, TDMAH, TDMAS, or Tris-DMAS) can be pressurized to deliver a liquid precursor to the syringe valve system 20. Typically, the tank 206 containing the liquid precursor can be pressurized to a pressure of from about 138 kPa (about 20 psi) to about 414 kPa (about 60 psi) and can be heated to a temperature of about 100 ° C or less. In one embodiment, 23 200822191 this temperature is from about 20 ° C to about 60 ° C. The syringe wide system 210 combines the liquid precursor with the carrier gas to form a precursor vapor that is injected into the process chamber 202. The carrier gas can include nitrogen, argon, helium, hydrogen, or combinations thereof, and the carrier gas can be preheated to a temperature of from about 85 t to about 150 °C.

The oxidizing gas system containing water vapor is introduced into the process chamber 2020 at a flow rate of from about 20 s c c m to about 1 00 s c c m . In one embodiment, the flow rate is from about 50 s c c m to about 200 s c c m. The oxidizing gas system is pulsed into the process chamber 202 at a rate of from about 0.1 second to about 10 seconds, depending on the particular process conditions and the desired composition of the deposited ruthenium containing material. In one embodiment, the oxidizing gas system is pulsed in at a rate of from about 1 second to about 3 seconds (e.g., about 1.7 seconds). In another embodiment, the oxidizing gas system is pulsed in at a rate of from about 0. 1 second to about 1 second (e.g., about 0.5 seconds). Oxidizing gas may be generated by WVG system 204, which is in fluid communication with process chamber 202 via conduit 214. Each of the hydrogen source gas (e.g., H2) and the oxygen source gas (e.g., 02) flows independently into the W V G system 220 at a flow rate of from about 20 seem to about 300 s c c m . The flow rate of the oxygen source gas can be higher than the flow rate of the hydrogen source gas. In one example, the hydrogen source gas can have a flow rate of about 10 s c c m and the oxygen source gas can have a flow rate of about 1 20,000 seem to enrich the water vapor with oxygen. In some embodiments, an alternative oxidizing gas (e.g., a conventional oxidizing agent) can be used to replace the oxidizing gas of the aqueous vapor formed from the WVG system. Alternative oxidizing gas systems that can be introduced into the process chamber from an aqueous oxygen source (not produced from a WVG system) include oxygen, ozone, atomic oxygen, hydrogen peroxide, nitrous oxide, nitric oxide, and nitrous oxide , 2 24 200822191 Nitric oxide, derivatives thereof, or combinations thereof. While embodiments of the present invention provide a process that can benefit from the oxidizing gas of water vapor generated by the WV G system, other embodiments provide an alternative to the formation of germanium-containing materials and other dielectric materials during the deposition processes described herein. Process for oxidizing gases or traditional oxidants. Ο

Exemplary ruthenium precursors include ruthenium containing ligands such as, for example, an image, an alkylamine, a cyclopentadienyl group, an alkyl group, an alkoxide, a derivative thereof, or a combination thereof. The hafnium halide compound which can be used as a ruthenium precursor includes HfCl4, Hfl4, HfBr4. The hafnium alky 1 amino compound which can be used as a ruthenium precursor includes (RR'N)4Hf, wherein R or R' is hydrogen, methyl, ethyl, propyl or butyl. The ruthenium precursor suitable for depositing ruthenium-containing material includes (Et2N)4Hf, (Me2N)4Hf, (MeEtN)4Hf, (ιΒιι(:5Η4)2ΗΜ12, (C5H5)2HfCl2, (EtC5H4)2HfCl2, (Me5C5)2HfCl2, ( Me5C5)HfCl3, (iPrC5H4)2HfCl2 ' (iprCsDHfCh, (acac)4Hf, (hfac)4Hf, (tfac)4Hf, (thd)4Hf, (N03)4Hf, CBuOhHf, (ipr〇)4Hf, (EtO)4Hf, (MeO) 4Hf, or a derivative thereof. In one embodiment, the ruthenium precursor system used during the deposition process includes HfCl4, (Et2N)4Hf or (Me2N)4Hf. An exemplary ruthenium precursor suitable for depositing ruthenium containing materials The material includes decane, alkylamine decane, decyl alcohol, or alkoxy decane. For example, the ruthenium precursor may include (Me2N)4Si, (Me2N)3SiH, (Me2N)2SiH2, (Me2N)SiH3, (Et2N)4Si, ( Et2N)3SiH, (MeEtN)4Si, (MeEtN)3SiH, 25 200822191

Si(NCO)4, MeSi(NCO)3, SiH4, Si2H6, SiCl4, Si2Cl6, MeSiCh, HSiCl3, Me2SiCl2, H2SiCl2, MeSi(OH)3, Me2Si(OH)2, (MeO)4Si, (EtO)4Si, Or a derivative thereof. Other alkylamine decane compounds which can be used as the ruthenium precursor include (RR'N)4_nSiHn wherein R or R' is hydrogen, methyl, ethyl, propyl or butyl, and n = 0-3. Other alkoxydecanes may be represented by the general chemical formula (RO) 4-nSiLn where R is a gas, methyl, ethyl, propyl or butyl group, and L is H, OH, F, Cl, Br or I, and mixtures thereof. In addition, higher decane is used as a ruthenium precursor in some embodiments of the invention. A higher decane series is disclosed in commonly assigned U.S. Patent Publication No. 2 0 04/0 2,240, the disclosure of which is incorporated herein by reference. In one embodiment, the hafnium precursor used during the deposition process comprises (Me2N)3SiH, (Et2N)3SiH, (Me2N)4Si, (Et2N)4Si or SiH4. Exemplary nitrogen precursors can include: NH3, N2, a hydrazine (eg, N2H4 or MeN2H3), an amine (eg, Me3N, Me2NH, or MeNH2), an aniline (eg, C^HsNH2), an organic azide (eg, MeN3 or Me3SiN3), an inorganic azide (for example, NaN3 or Cp2CoN3), a radical nitrogen compound (for example, N 3 , N 2 , N, N Η or N Η 2 ), a derivative thereof, or a combination thereof. Free radical nitrogen compounds can be produced by heat, hot wires or electrical equipment. In an embodiment, the precursor is a liquid. The liquid precursor can be delivered to the chamber 100 by a direct injection method. Some useful precursors include flammable precursors, pyrophoric precursors, and toxic precursors. Suitable flammable precursors include HfCU, La(THD)2, 26 200822191

Pr(THD)3, Pr(N(SiMe3)2)3, La(N(SiMe3)2)3),

La(i-Pr-AMD)3, TAETO, TDMAH, DMAH and TMAI are used as solid precursors. Combustible liquid precursors include TDEAHf, TDEAZr, TEMAHf, TEMAZr, 4-DMAS, 3-DMAS, TBTDET, TBTEMT, IPTDET, IPTEMT, DMEEDMAA, EBDA, TDEAS, TEMAS and BTBAS. Suitable viscous and pyrophoric precursors include Me3A1, Me2AlH and other organoaluminum compounds. Suitable for toxic or pyrophoric or reactive gases

The ruthenium precursor includes AsH3, GeH4, SiH4, NH3, PH3, Si2H6, B2H6, NO, dichlorodecane, hexachlorodecane, and NW. These precursors can be delivered at room temperature to about 300 ° C by bubble formation or through a liquid delivery system. The solid precursor can be heated by covering the precursor source with a heater strip or heater jacket to ensure that the precursor maintains the liquid form. A heater jacket or belt can be placed on top of the solid precursor source to prevent leakage of the precursor and contact with the heater jacket. When using toxic, flammable or ignited precursors, it is beneficial to utilize a venting system to ensure that harmful gases do not accumulate within the chamber components. For example, when the technician must maintain the gas disk 208, the precursor gas may have leaked into the faceplate. Due to the high temperature of the chamber 100, the precursor may ignite, and thus the technician or others may be humiliated. Therefore, a discharge conduit 22 can be coupled to the gas faceplate 208. The ® ψ # ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 222 222 222 222 222 222 222 222 222 222 222 222 222 222 222 222 222 222 222 222 The exhaust port can be coupled to a discharge fan. 206 when maintenance is required. A discharge conduit Similarly, when the hazardous gases of the tank are beneficial, the removal of any accumulated 224 can be coupled to the tank 27 200822191 206 to discharge the hazardous gases out of the tank 206. The exhaust conduit 224 may have a valve 226 connected thereto, and the valve 226 may discharge gas when it is opened. In another embodiment, the water vapor generator system 204 can have a discharge conduit 228 that is vented via an open valve 226. A discharge conduit 228 coupled to the steam generator system 204 can vent the leaked body. By providing the exhaust conduits 222, 24, 228, the chamber 100 can handle combustible, toxic, and pyrophoric precursors in a safe and efficient manner. While the foregoing description focuses on embodiments of the present invention, the present invention and further The embodiments can be constructed without departing from the basic scope of the invention, and the scope of the invention is determined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing features of the invention may be further understood by reference to the exemplary embodiments. It is to be understood, however, that the appended claims BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing an apparatus according to an embodiment of the present invention. Figures 2A and 2B are schematic views of a processing system in accordance with an embodiment of the present invention. Figure 3 is a diagram of a processing system according to another embodiment of the present invention, which is intended to be harmful to water and gas. 28 200822191

[Major component symbol description] 100 Process chamber 102 Source 104 Water vapor generator system 106 Gas panel 108 Catheter system 110 Catheter system 112 Valve 114 Gas inlet 116 Expansion channel 118 Tip 120 Cover 122 Funnel lining 124 Protruding surface 126 Fixings 128 retaining ring lining 130 purification line 132 upper process lining 134 slit wide 136 slit valve lining 140 wall surface 142 heat blocking plate 146 into π 148 chamber body 150 vacuum system 152 thirsty wheel molecular pump 154 discharge adapter 156 Clogged gap 160 vacuum 埠 162 lower process lining 164 substrate support carrier 166 substrate 168 adapter 170 thermal insulation 172 hood 174 heater 176 heater bar 202 process chamber 204 WVG system 206 tank 208 gas panel 210 Syringe valve system 212 fitting fitting 214 conduit 216 fitting fitting 218 conduit 220 distance 29 200822191 222 discharge conduit 22 4 discharge conduit 226 valve 228 discharge conduit 230 gas turbine 232 gas sensor 234 contact 236 catalyst reaction β 238 gas filter 240 gas input π 242 conduit system 244 hydrogen source 246 carrier gas source 248 oxygen source

30

Claims (1)

200822191 X. Patent Application Range: 1. A vapor deposition apparatus comprising at least: a liquid precursor or solid precursor delivery cabinet having a discharge line coupled thereto; • a gas face plate having a discharge line Coupled thereto; a water vapor generator system having a discharge line coupled thereto; and f) one or more toxic, flammable or ignited precursor sources. 2. The device of claim 1, further comprising a plurality of heater bars coupled to a cover of the device. 3. The apparatus of claim 1, further comprising a turbo molecular pump coupled to the device. 4. The apparatus of claim 1, further comprising a chamber having a liner coupled thereto. 4 5. The apparatus of claim 4, wherein the lining comprises stainless steel, quartz, inscription, sapphire 'graphite, or ceramic material. 6. The apparatus of claim 5, wherein the liner is coated with PBN, SiC, quartz, or aluminum. The apparatus of claim 1, wherein the apparatus is an atomic layer deposition apparatus. 8. The apparatus of claim 1, wherein the apparatus is a chemical vapor deposition apparatus. 9. The device of claim 1, further comprising a heat exchanger coupled to the device. 1 〇. The device of claim 1, further comprising a pair of blocks of heated carriers that are transferred to the device. 11. A vapor deposition method comprising at least: Introducing at least one precursor to a device having a liquid precursor or solid precursor delivery cabinet, a gas faceplate, and a water vapor generator system selected from the group consisting of toxic precursors, flammable precursors, and igniting a group of precursors; expelling precursor gases from at least one of the liquid delivery cabinet, the gas faceplate, or the water vapor generator system; and depositing a layer on a substrate. 12. The method of claim 11, wherein the toxic precursor 32 200822191 is selected from the group consisting of ASH3, GeH4, SiH4, NH3, PH3, Si2H6, B2H6, NO, dichloromethane, hexachloroantane, and Νπ The group that is formed. The method of claim 11, wherein the flammable precursor is selected from the group consisting of HfCl4, La(THD)2, Pr(THD)3, Pr(N(SiMe3)2)3, La(N) (SiMe3) 2) 3), La(i-Pr-AMD) 3, TAETO, TDMAH, DMAH, and TMAI. The method of claim 11, wherein the flammable precursor is selected from the group consisting of TDEAHf, TDEAZr, TEMAHf, TEMAZr, 4-DMAS, 3-DMAS, TBTDET, TBTEMT, IPTDET, IPTEMT, DMEEDMAA, EBDA, TDEAS, TEMAS, and BTBAS groups. 15. The method of claim 11, wherein the pyrophoric precursor is selected from the group consisting of Me3Ah Me2AlH and an organoaluminum compound. The method of claim 11, wherein the precursor is a liquid precursor, and the method further comprises directly injecting the liquid precursor. The method of claim 11, wherein the layer is deposited by an atomic layer deposition method. 33. The method of claim 11, wherein the layer is deposited by chemical vapor deposition. The method of claim 11, wherein the deposited layer is a high-k dielectric layer or a metal gate layer. 20. The method of claim 11, wherein the deposited layer comprises a layer. U 34