WO2005117087A1 - Formation of a silicon oxynitride layer on a high-k dielectric material - Google Patents
Formation of a silicon oxynitride layer on a high-k dielectric material Download PDFInfo
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- WO2005117087A1 WO2005117087A1 PCT/US2005/016690 US2005016690W WO2005117087A1 WO 2005117087 A1 WO2005117087 A1 WO 2005117087A1 US 2005016690 W US2005016690 W US 2005016690W WO 2005117087 A1 WO2005117087 A1 WO 2005117087A1
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
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- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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Definitions
- Embodiments of the invention generally relate to methods for depositing materials on substrates, and more specifically, to methods for depositing capping layers, such as silicon oxides or silicon oxynitrides, onto dielectric materials.
- ALD atomic layer deposition
- reactant gases are sequentially introduced into a process chamber containing a substrate.
- a first reactant is pulsed into the process chamber and is adsorbed onto the substrate surface.
- a second reactant is pulsed into the process chamber and reacts with the first reactant to form a deposited material.
- a purge step is typically carried out between the delivery of each reactant gas. The purge step may be a continuous purge with the carrier gas or a pulse purge between the delivery of the reactant gases.
- silicon nitride materials have been used as an effective boron barrier layer at the dielectric/gate interface.
- silicon nitride materials may have poor device properties due to inherently fixed charges.
- a desirable barrier layer should form the dielectric/gate interface and enhances the mobility of charge carriers in the polysilicon by blocking dopant diffusion from the polysilicon layer.
- ALD processes have been used to deposit thin silicon oxide layers onto substrates. Silicon oxide layers deposited by an ALD process, plasma treated and subsequently annealed have been utilized as capping layers. However, silicon oxide layers are often deposited by ALD processes that alternate pulses of dichlorosilane (CI 2 SiH 2 ) with water or oxygen. The silicon oxide may be contaminated with halogen impurities due to the chlorinated silane precursors. If silicon oxide layers contaminated with halogens are used as dopant barrier layers, chlorine may diffuse into the polysilicon layer adversely effecting the charge carrier mobility.
- a deposition process to cap a dielectric material with a barrier layer, such as silicon oxide or silicon oxynitride.
- the barrier layer should be free of halogen contamination and be as thin as possible while reducing dopant diffusion, as well as the barrier layer and the dielectric layer should be chemically compatible.
- a method for depositing a capping layer on a dielectric layer disposed on a substrate includes exposing a substrate to a deposition process to form a dielectric layer thereon and exposing the substrate to sequential pulses of a silicon precursor and an oxidizing gas to form a silicon-containing layer on the dielectric layer during a deposition process.
- the method further provides exposing the substrate to a nitridation process to form a capping layer thereon and optionally exposing the substrate to an annealing process for a predetermined time.
- the capping layer may have a thickness of about 5 A or less.
- the oxidizing gas contains water vapor derived from a hydrogen source gas and an oxygen source gas processed by a water vapor generator containing a catalyst.
- the dielectric layer may contain HfO 2 , HfSiO , HfSi ⁇ OyN 2 , HfAl ⁇ OyN z , AI 2 O 3 , HfO 2 /AI 2 O 3 laminate, LaAIO x , LaO x , derivatives thereof or combinations thereof.
- the capping layer is exposed to a nitrogen- containing plasma during the nitridation process.
- the deposition, nitridation and annealing processes occur in the same process chamber.
- a method for depositing a capping layer on a dielectric layer in a process chamber includes depositing a dielectric layer on a substrate, exposing the dielectric layer to sequential pulses of a silicon precursor and an oxidizing gas during an ALD process to deposit a silicon- containing layer on the dielectric layer and exposing the silicon-containing layer to a nitridation process to form a 'capping layer.
- the method further provides exposing the substrate to an annealing process and subsequently, depositing a polysilicon layer on the capping layer.
- a method for depositing a silicon-containing capping layer on a dielectric layer by an atomic layer deposition process includes positioning a substrate containing a dielectric layer within a process chamber, exposing the substrate to a silicon precursor, purging the process chamber with a purge gas, exposing the substrate to an oxidizing gas containing water vapor.
- the water vapor formed from a hydrogen source gas and an oxygen source gas by a water vapor generator containing a catalyst and purging -the process chamber with the purge gas.
- a method for depositing a capping layer on a dielectric layer in a process chamber includes depositing a metal silicate material on a substrate during a first ALD process cycle that contains sequentially introducing a metal precursor pulse, a first oxidizing gas pulse, a silicon precursor pulse and a second oxidizing gas pulse.
- the method further provides altering the first ALD process cycle by stopping the metal precursor pulse and the first oxidizing gas pulse to form a second ALD process cycle and depositing a silicon oxide layer on the metal silicate material during the second ALD process cycle that contains sequentially introducing the silicon precursor pulse and the second oxidizing gas pulse.
- the oxidizing gas may contain water vapor formed by flowing a hydrogen source gas and an oxygen source gas through a water vapor generator.
- the process includes a hafnium precursor a hafnium silicate material.
- the metal silicate material may contain aluminum, nitrogen or lanthanum.
- a polysilicon layer optionally containing a dopant e.g., boron, phosphorus or arsenic may be deposited on the silicon oxynitride layer.
- Figure 1 illustrates a process sequence for forming a capping layer on a dielectric layer according to one embodiment described herein;
- Figures 2A-2F illustrate a process sequence for depositing multiple layers on a substrate surface according to another embodiment described herein;
- Figure 3 illustrates ALD pulsing sequences for the silicon precursor and oxidizing gas according to one embodiment described herein;
- Figure 4 depicts a schematic cross-sectional view of a process chamber that may be used to perform an ALD process described herein.
- Embodiments of the invention provide methods for preparing dielectric materials used in a variety of applications, especially for high-k dielectric materials used in transistor and capacitor fabrication. Some of the processes use atomic layer deposition (ALD) techniques to control elemental composition of the deposited dielectric materials.
- Embodiments provide a method for preparing silicon-containing layers (e.g., silicon oxides) used as a capping barrier layer on high-k dielectric materials.
- the process includes a water vapor generator to produce an oxidizing gas that contains water vapor.
- a silicon precursor and the oxidizing gas are sequentially pulsed during an ALD process to deposit silicon-containing material.
- the ALD process utilizes the water vapor to form silicon-containing layers neatly and efficiently, thereby significantly increasing production throughput.
- silicon-containing layers are exposed to a nitrogen plasma during a nitridation process (e.g., decoupled plasma nitridation (DPN)) and subsequently exposed to an annealing process.
- DPN decoupled plasma
- FIG 1 illustrates an exemplary process sequence 100 for forming a capped dielectric film, such as a silicon oxide layer on a high-k gate dielectric material.
- Figures 2A-2F correspond to process sequence 100 to illustrate the assembly of a semiconductor device, such as a transistor.
- dielectric layer 210 is deposited on substrate 200, depicted in Figures 2A-2B, by conventional deposition techniques, such as ALD, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal techniques or combinations thereof.
- dielectric layer 210 may be deposited by an ALD process and an ALD apparatus, such as described in co-pending United States Provisional Patent Application Serial No.
- Dielectric layer 210 is generally deposited with a film thickness in a range from about 10 A to about 1 ,000 A, preferably from about 20 A to about 500 A and more preferably from about 50 A to about 200 A, for example, about 100 A.
- substrate 200 may be exposed to a pretreatment process in order to terminate the substrate surface with a variety of functional groups.
- the pretreatment process may expose the substrate to a reagent, such as NH 3 , B 2 H 6 , SiH 4 , SiH 6 , H 2 O, HF, HCI, O 2 , O 3 , H 2 O, H 2 O 2 , H 2 , atomic-H, atomic-N, atomic-O, alcohols or amines.
- the functional groups may provide a base for an incoming chemical precursor to attach on the substrate surface.
- the pretreatment process may expose the substrate surface to the reagent for a period in a range from about 5 seconds to about 2 minutes, preferably from about 10 seconds to about 30 seconds. In one example, the substrate surface is exposed to water vapor derived from a WVG system for about 15 seconds prior to starting an ALD process.
- Dielectric layer 210 is deposited on the substrate surface and may have a variety of compositions that are homogenous, heterogeneous, graded and/or multiple layered stacks or laminates.
- Dielectric layer 210 is generally a high-k dielectric material and may include combinations of hafnium, zirconium, titanium, tantalum, lanthanum, aluminum, silicon, oxygen and/or nitrogen.
- Dielectric layer 210 may have a composition that includes hafnium-containing materials, such as hafnium oxides (HfO x or HfO 2 ), hafnium silicates (HfSi x O y or HfSiO 4 ), hafnium silicon oxynitrides (HfSi x O y Nz), hafnium oxynitrides (HfO x N y ), hafnium aluminates (HfAl x O y ), hafnium aluminum silicates (HfAl x Si y O z ), hafnium aluminum silicon oxynitrides
- hafnium-containing materials such as hafnium oxides (HfO x or HfO 2 ), hafnium silicates (HfSi x O y or HfSiO 4 ), hafnium silicon oxynitrides (HfSi x O y Nz), hafnium oxyn
- hafnium lanthanum oxides HfLa x O y
- zirconium-containing materials such as zirconium oxides (ZrO x or ZrO 2 ), zirconium silicates (ZrSi x O y or
- ZrSiO 4 zirconium silicon oxynitrides (ZrSi ⁇ O y N z ), zirconium oxynitrides (ZrO x N y ), zirconium aluminates (ZrAl x O y ), zirconium aluminum silicates (ZrAl x SiyO z ), zirconium aluminum silicon oxynitrides (ZrAl w Si x O y N z ), zirconium lanthanum oxides (ZrLa x O y ), other aluminum-containing materials or lanthanum-containing materials, such as aluminum oxides (AI 2 O 3 or AIO x ), aluminum oxynitrides (AIO x N y ), aluminum silicates (AISi x Oy), aluminum silicon oxynitrides (AISi x O y N 2 ), lanthanum aluminum oxides (LaAl ⁇ O y ), lanthanum oxides (LaO x
- dielectric materials useful for dielectric layer 210 may include titanium oxides (TiO x or TiO 2 ), titanium oxynitrides (TiO x N y ), tantalum oxides (TaO x or Ta 2 O 5 ) and tantalum oxynitrides (TaO x N y ).
- Laminate films that are useful dielectric materials for dielectric layer 210 include HfO 2 /AI 2 O 3 , HfO 2 /SiO 2 , La 2 Os/AI 2 O 3 and HfO 2 /SiO 2 /AI 2 O 3 .
- silicon oxide layer 220 is deposited on dielectric layer 210 by , an ALD process, as depicted in Figure 2C.
- Silicon oxide layer 220 may include silicon dioxide (SiO 2 ) or other silicon oxides (SiO x ), such as less oxidized forms.
- silicon oxide layer 220 is deposited with a thickness in a range from about 1 A to about 20 A, preferably from about 2 A to about 10 A, and more preferably from about 3 A to about 8 A, for example, about 5 A. In many embodiments, silicon oxide layer 220 has a thickness of about 5 A or less.
- dielectric layer 210 Prior to the deposition of silicon oxide layer 220, dielectric layer 210 may be exposed to a pretreatment process similarly disclosed for pretreatment of substrate 200 prior to the deposition of dielectric layer 210.
- the substrate is loaded into a process chamber capable of performing cyclical deposition and the process conditions are adjusted by setting the predetermined temperature, pressure and flow rate of the carrier gas.
- the process chamber used to deposit silicon oxide layer 220 is the same process chamber used to deposit dielectric layer 210.
- a first process chamber is used to deposit dielectric layer 210 and a second process chamber is used to deposit silicon oxide layer 220.
- the first process chamber and the second process chamber may be on different cluster tools, but preferably on the same cluster tool.
- FIG. 3 illustrates ALD process 300 forms a silicon oxide layer 220, according to one embodiment of the invention.
- dielectric layer 210 on the substrate surface is exposed to pulse of a silicon precursor that is introduced into the process chamber for a time period in a range from about 0.1 seconds to about 5 seconds.
- a pulse of purge gas is then introduced into the process chamber to purge or otherwise remove any residual silicon precursor or by-products in step 304.
- a pulse of oxidizing gas is introduced into the process chamber.
- the oxidizing gas may include several agents, such as water vapor, oxygen.
- a pulse of purge gas is then introduced into the process chamber to purge or otherwise remove any residual oxidizing gas or by-products in step 308.
- Suitable carrier gases or purge gases may include helium, argon, nitrogen, hydrogen, forming gas, oxygen or combinations thereof.
- silicon oxide layer 220 is formed having a particular thickness. Generally, about 8 ALD process cycles are completed to form silicon oxide layer 220 with a thickness of about 5 A. Depending on specific device requirements, subsequent deposition cycles may be needed to deposit silicon oxide layer 220 having a predetermined thickness in step 310. In step 312, once the predetermined thickness of silicon oxide layer 220 is achieved, ALD process 300 is ceased.
- the cyclical deposition process or ALD process typically occurs in a process chamber at a pressure in the range from about 1 Torr to about 100 Torr, preferably from about 1 Torr to about 20 Torr, for example, about 10 Torr.
- the substrate may be heated to a temperature is in the range from about 70°C to about 1 ,000°C, preferably from about 100°C to about 450°C, and more preferably from about 200°C to about 400°C.
- the silicon precursor is introduced into the process chamber with a flow rate in the range from about 5 standard cubic centimeters per minute (seem) to about 200 seem.
- the silicon precursor is usually introduced with a carrier gas, such as nitrogen, with a total flow rate in the range from about 50 seem to about 1 ,000 seem.
- the silicon precursor is pulsed into the process chamber at a rate in a range from about 0.1 seconds to about 10 seconds, depending on the particular process and desired silicon oxide layer 220. In an embodiment with a long pulse, the silicon precursor is pulsed at a rate in a range from about 1 second to about 5 seconds, for example, about 3 seconds.
- the silicon precursor is pulsed at a rate in a range from about 0.1 seconds to about 1 second, for example, about 0.5 seconds.
- the silicon precursor is preferably tetrakis(dimethylamino)silane ((Me 2 N) 4 Si or TDMAS) or tris(dimethylamino)silane ((Me 2 N) 3 SiH or Tris-DMAS).
- the oxidizing gas is introduced to the process chamber with a flow rate in the range from about 20 seem to about 1 ,000 seem, preferably from about 50 seem to about 200 seem.
- the oxidizing gas is pulsed into the process chamber at a rate in a range from about 0.1 seconds to about 10 seconds, depending on the particular process.
- the oxidizing gas is pulsed at a rate in a range from about 1 second to about 5 seconds, for example, about 1.7 seconds.
- the oxidizing gas is pulsed at a rate in a range from about 0.1 seconds to about 3 seconds, for example, about 0.5 seconds.
- the oxidizing gas may be produced from a water vapor generating (WVG) system that is in fluid communication to the process chamber.
- WVG water vapor generating
- the WVG system generates ultra-high purity water vapor by means of a catalytic reaction of an oxygen source gas (e.g., O 2 ) and a hydrogen source gas (e.g., H 2 ).
- the hydrogen and the oxygen each may flow into the WVG system at a rate in the range from about 20 seem to about 200 seem.
- the flow of oxygen is higher than the flow of hydrogen to have an excess of oxygen, for example, the hydrogen has a flow rate of about 100 seem and oxygen has a flow rate of about 120 seem. Therefore, the water vapor flowing out of the WVG system is enriched with oxygen.
- the hydrogen has a flow rate of about 100 seem and the oxygen has a flow rate of about 120 seem to produce an oxidizing gas containing water vapor with a flow rate of about 100 seem and oxygen with a flow rate of about 70 seem.
- a preferred hydrogen/oxygen concentration may be experimentally determined for each individual process to adjust the outward flow of oxidizing gas containing water vapor and oxygen or hydrogen.
- hydrogen has a flow rate of about 50 seem and oxygen has a flow rate of about 60 seem.
- the WVG system has a catalyst-lined reactor or a catalyst cartridge in which water vapor is generated by means of a chemical reaction, unlike pyrogenic generators that produce water vapor as a result of ignition.
- the catalyst may include a metal or alloy, such as palladium, platinum, nickel, combinations thereof or alloys thereof.
- the ultra-high purity water is ideal for the ALD processes in the present invention.
- oxygen is allowed to flow through the WVG system for about 5 seconds.
- hydrogen is allowed to enter the reactor for about 5 seconds.
- the catalytic reaction between hydrogen and oxygen is instantaneous, so water vapor is generated immediately after the hydrogen and oxygen reach the reactor.
- the oxidizing gas may contain water vapor, hydrogen, oxygen or combinations thereof.
- the oxidizing gas contains water vapor and oxygen.
- the oxidizing gas contains water vapor and hydrogen.
- the amount of water vapor may also be regulated, yielding accurate and repeatable flows every time.
- water vapor is usually generated by flowing hydrogen and oxygen into the WVG system.
- An oxygen source gas useful to generate an oxidizing gas containing water vapor may include oxygen (O 2 ), atomic oxygen (O), ozone (O 3 ), nitrous oxide
- a hydrogen source gas useful to generate an oxidizing gas containing water vapor may include hydrogen (H 2 ), atomic hydrogen (H), forming gas (N 2 /H 2 ), ammonia (NH 3 ), hydrocarbons (e.g., CH ), alcohols (e.g., CH 3 OH), derivatives thereof or combinations thereof.
- a carrier gas may be co-flowed with either the oxygen source gas or the hydrogen source gas and may include N 2 , He, Ar or combinations thereof.
- the oxygen source gas is oxygen or nitrous oxide and the hydrogen source gas is hydrogen or a forming gas, such as 5 vol% hydrogen in nitrogen.
- Suitable WVG systems are commercially available, such as the WVG by Fujikin of America, Inc., located in Santa Clara, California, and the CSGS (Catalyst Steam Generator System) by Ultra Clean Technology, located in Menlo Park, California.
- the pulses of a purge gas or carrier gas, preferably argon or nitrogen, at steps 304 and 308, are typically introduced with a flow rate in a range from about 2 standard liters per minute (slm) to about 22 slm, preferably about 10 slm.
- the purge gas or carrier gas is introduced into the process chamber with a flow rate in a range from about 0.1 seconds to about 10 seconds, depending on the particular process.
- the purge gas or carrier gas is pulsed at a rate in a range from about 1 second to about 5 seconds, for example, about 1.7 seconds.
- the purge gas or carrier gas is pulsed at a rate in a range from about 0.1 seconds to about 3 seconds, for example, about 0.5 seconds.
- Each processing cycle (steps 302 through 308) may last for a time period in a range from about 0.01 seconds to about 20 seconds. For example, in an embodiment of a long cycle, the processing cycle lasts about 10 seconds, while in an embodiment of a short cycle, the processing cycle lasts about 2 seconds.
- the specific pressures and times are obtained through routine experimentation. In one example, a 300 mm diameter wafer needs about twice the flow rate as a 200 mm diameter wafer in order to maintain similar throughput.
- hydrogen gas is applied as a carrier gas, purge and/or a reactant gas to reduce halogen contamination from the deposited material during an ALD process.
- a reactant gas e.g., CI 2 SiH 2 , SiCI or Si 2 CI 6
- halogen atoms e.g., CI 2 SiH 2 , SiCI or Si 2 CI 6
- Hydrogen is a reductant and will produce hydrogen halides (e.g., HCI) as a volatile and removable byproduct. Therefore, hydrogen may be used as a carrier gas or reactant gas when combined with a precursor compound (e.g., silicon or oxygen precursors) and may include another carrier gas (e.g., Ar or N 2 ).
- a water/hydrogen mixture at a temperature in a range from about 100°C to about 500°C, is used to reduce the halogen concentration and increase the oxygen concentration of a deposited silicon oxide layer during ALD processes described herein.
- Many silicon precursors are within the scope of the invention.
- One important precursor characteristic is to have a favorable vapor pressure.
- Precursors at ambient temperature and pressure may have gas, liquid or solid states. However, volatilized precursors are utilized within the ALD chamber.
- silicon precursors include silanes, alkylsilanes, alkylaminosilanes, silanols, and alkoxy silanes
- silicon precursors include (Me 2 N) 4 Si, (Me 2 N) 3 SiH, (Me 2 N) 2 SiH 2 , (Me 2 N)SiH 3 , (Et 2 N) 4 Si, (Et 2 N) 3 SiH, (MeEtN) 4 Si, (MeEtN) 3 SiH, Si(NCO) 4 , MeSi(NCO) 3 , SiH 4 , Si 2 H 6l SiCI 4 , Si 2 CI 6 , MeSiCI 3 , HSiCI 3 , Me 2 SiCI 2 , H 2 SiCI 2 , MeSiH 3 , Me 2 SiH 2 , EtSiH 3l Et 2 SiH 2 , MeSi(OH) 3 , Me 2 Si(OH) 2 , (EtO) 4 Si, derivative thereof,
- higher silanes are used as silicon precursors within some embodiments of the invention. Higher silanes are disclosed in commonly assigned United States Patent Application Serial No 10/688,797, filed on October 17, 2003, entitled, "Silicon- containing Layer Deposition with Silicon Compounds," published as US 20040224089, and is incorporated herein by reference in entirety for the purpose of describing silicon precursors.
- Preferred silicon precursors used during ALD processes herein include (Me 2 N) 3 SiH, (Et 2 N) 3 SiH, (Me 2 N) 4 Si, (Et 2 N) 4 Si, and (MeEtN) 4 Si.
- steps 102 and 104 are performed in the same ALD chamber by ceasing the flow of particular reagents, such as the metal precursor, used in step 102, and continuing the flow of other reagents, such as the silicon precursor and/or oxidizing gas.
- dielectric layer 210 contains hafnium silicate and is deposited as by an ALD process that includes sequentially pulsing HfCI , water vapor, TDMAS and water vapor, with each precursor separated by a purge during an ALD cycle. Dielectric layer 210 is formed by repeating the ALD cycle until the film has a thickness of about 100 A (step 102).
- the ALD cycle is altered by stopping the HfCI 4 half reaction and one of the water vapor half reactions and continuing the TDMAS half reaction and the other water vapor half reaction.
- the ALD process (step 104) proceeds by sequentially pulsing TDMAS and water vapor, with each precursor separated by a purge cycle. After about 8 cycles of the ALD process, silicon oxide layer 220 with a thickness of about 5 A is formed on dielectric layer 210 containing the hafnium silicate.
- the substrate may be transferred to a decoupled plasma nitridation (DPN) chamber, such as the CENTURATM DPN chamber, available from Applied Materials, Inc., located in Santa Clara, California.
- DPN decoupled plasma nitridation
- the DPN chamber is on the same cluster tool as the ALD chamber used to deposit dielectric layer 210 and/or the ALD chamber used to deposit silicon oxide layer 220. Therefore, the substrate may be exposed to a nitridation process without being exposed to the ambient environment.
- Silicon oxide layer 220 is exposed to a nitridation process to physically incorporate nitrogen atoms into the silicon oxide material forming nitrogen-containing silicon oxide layer 230, as depicted in Figure 2D.
- the nitrogen concentration of nitrogen-containing silicon oxide layer 230 may be in the range from about 5 atomic percent (at%) to about 40 at%, preferably from about 10 at% to about 25 at%.
- the nitridation process exposes silicon oxide layer 220 to nitrogen plasma, such as a DPN process.
- nitrogen plasma such as a DPN process.
- N 220 is bombarded with atomic-N formed by co-flowing N 2 and a noble gas plasma, such as argon.
- a noble gas plasma such as argon.
- nitrogen-containing gases may be used to form the nitrogen plasma, such as NH 3 , hydrazines (e.g., N 2 H 4 or MeN 2 H 3 ), amines (e.g.,
- Me 3 N, Me 2 NH or MeNH 2 Me 3 N, Me 2 NH or MeNH 2
- anilines e.g., C 6 H 5 NH 2
- azides e.g., MeN 3 or
- nitridation process proceeds at a time period within a range from about 10 seconds to about 120 seconds, preferably from about 15 seconds to about 60 seconds, for example, about 30 seconds. Also, the nitridation process is conducted with a plasma power setting at about 900 watts to about 2,700 watts and a pressure at about 10 mTorr to about 100 mTorr. The nitrogen has a flow from about 0.1 slm to about 1.0 slm, while the noble gas has a flow from about 0.1 slm to about 1.0 slm. In a preferred embodiment, the nitridation process is a DPN process and includes a plasma by co-flowing Ar and N 2 .
- a nitridation process may include exposing silicon oxide layer 220 to nitrogen plasma during each ALD half reaction, at the completion of an ALD cycle and/or at the completion of the deposition of silicon oxide layer 220.
- a nitridizing remote-plasma is exposed to silicon oxide layer 220 to form nitrogen- containing silicon oxide layer 230 directly in the ALD process chamber. Radical nitrogen compounds may also be produced by heat or hot-wires and used during nitridation processes.
- nitrogen-containing silicon oxide layer 230 Other nitridation processes to form nitrogen-containing silicon oxide layer 230 are contemplated, such as annealing the substrate in a nitrogen- containing environment, and/or including a nitrogen precursor into an additional half reaction within the ALD cycle while forming nitrogen-containing silicon oxide layer 230.
- an additional half reaction during an ALD cycle to form silicon oxide may include a pulse of NH 3 followed by a pulse of purge gas.
- the substrate is subsequently transferred to an annealing chamber, such as the CENTURATM RADIANCETM RTP chamber available from Applied Materials,
- the substrate may be annealed without being exposed to the ambient environment.
- step 108 the substrate is annealed converting nitrogen-containing silicon oxide layer 230 to capping layer
- the substrate is heated to a temperature within a range from about 600°C to about 1 ,200°C, preferably from about 800°C to about 1 ,100°C for a time period within a range from about 1 second to about 120 seconds, preferably from about 30 seconds to about 90 seconds, for example, at about 1 ,000°C for about 60 seconds.
- the annealing chamber atmosphere contains at least one anneal gas, such as O 2 , N 2 ,
- the annealing chamber is maintained at a pressure in a range from about 5 Torr to about 100 Torr, for example, at about 15 Torr.
- the nitrogen atoms within nitrogen-containing silicon oxide layer 230 are chemically incorporated into capping layer 240.
- capping layer 240 may be deposited thereon, such as polysilicon layer 250, as shown in Figure 2F.
- Polysilicon layer 250 may be deposited by CVD, atomic layer epitaxy (ALE), thermal decomposition methods, or similar deposition techniques known in the art.
- Polysilicon layer 250 generally contains dopants, such as boron, phosphorus or arsenic. Capping layer 240 maintains a dopant barrier at interface 245 between dielectric layer 210 and polysilicon layer 250, thus the mobility of charge carriers is enhanced in a boron- doped, polysilicon layer 250.
- FIG 4 is a schematic cross-sectional view of one embodiment of a process chamber 380 including a gas delivery apparatus 430 adapted for cyclic deposition, such as atomic layer deposition or rapid chemical vapor deposition.
- a gas delivery apparatus 430 adapted for cyclic deposition, such as atomic layer deposition or rapid chemical vapor deposition.
- a detailed description for a process chamber 380 is described in commonly assigned United Application Publication No. 20030121608, which is incorporated herein in their entirety by reference.
- Several alternative chambers for cyclic deposition are described in co-pending United States Provisional Patent Application Serial No. 60/570,173, filed May 12, 2004, entitled, "Atomic Layer Deposition of Hafnium- containing High-K Materials," assigned to Applied Materials, Inc., and is herein incorporated by reference.
- atomic layer deposition (ALD) and rapid chemical vapor deposition refer to the sequential introduction of reactants to deposit a thin layer over a substrate structure.
- the sequential introduction of reactants may be repeated to deposit a plurality of thin layers to form a conformal layer to a desired thickness.
- the process chamber 380 may also be adapted for other deposition techniques.
- the process chamber 380 comprises a chamber body 382 having sidewalls 384 and a bottom 386.
- a slit valve 388 in the process chamber 380 provides access for a robot (not shown) to deliver and retrieve a substrate 390, such as a semiconductor wafer with a diameter of 200 mm or 300 mm or a glass substrate, from the process chamber 380.
- a substrate support 392 supports the substrate 390 on a substrate receiving surface 391 in the process chamber 380.
- the substrate support 392 is mounted to a lift motor 414 to raise and lower the substrate support 392 and a substrate 90 disposed thereon.
- a lift plate 416 connected to a lift motor 418 is mounted in the process chamber 380 and raises and lowers pins 420 movably disposed through the substrate support 392.
- the pins 420 raise and lower the substrate 390 over the surface of the substrate support 392.
- the substrate support 392 may include a vacuum chuck, an electrostatic chuck, or a clamp ring for securing the substrate 390 to the substrate support 392 while processing the substrate 390.
- the substrate support 392 may be heated to increase the temperature of a substrate 390 disposed thereon.
- the substrate support 392 may be heated using an embedded heating element, such as a resistive heater, or may be heated using radiant heat, such as heating lamps disposed above the substrate support 392.
- a purge ring 422 may be disposed on the substrate support 392 to define a purge channel 424 which provides a purge gas to a peripheral portion of the substrate 390 to prevent deposition thereon.
- a gas delivery apparatus 430 is disposed at an upper portion of the chamber body 382 to provide a gas, such as a process gas and/or a purge gas, to the process chamber 380.
- a vacuum system 478 is in communication with a pumping channel 479 to evacuate any desired gases from the process chamber 380 and to help maintain a desired pressure or a desired pressure range inside a pumping zone 466 of the process chamber 380.
- the chamber depicted by Figure 4 permits the process gas and/or purge gas to enter the process chamber 380 normal (i.e., 90°) with respect to the plane of the substrate 390 via the gas delivery apparatus 430. Therefore, the surface of substrate 390 is symmetrically exposed to gases that allow uniform film formation on substrates.
- the process gas includes a silicon precursor (e.g., TDMAS) during one pulse and includes an oxidizing gas (e.g., water vapor) in another pulse.
- the gas delivery apparatus 430 comprises a chamber lid 432.
- the chamber lid 432 includes an expanding channel 434 extending from a central portion of the chamber lid 432 and a bottom surface 460 extending from the expanding channel 434 to a peripheral portion of the chamber lid 432.
- the bottom surface 460 is sized and shaped to substantially cover a substrate 390 disposed on the substrate support 392.
- the chamber lid 432 may have a choke 462 at a peripheral portion of the chamber lid 432 adjacent the periphery of the substrate 390.
- the cap portion 472 includes a portion of the expanding channel 434 and gas inlets 436A, 436B.
- the expanding channel 434 has gas inlets 436A, 436B to provide gas flows from two similar valves 442A, 442B. The gas flows from the valves 442A, 442B may be provided together and/or separately.
- valve 442A and valve 442B are coupled to separate reactant gas sources but are preferably coupled to the same purge gas source.
- valve 442A is coupled to reactant gas source 438 and valve 442B is coupled to reactant gas source 439, and both valves 442A, 442B are coupled to purge gas source 440.
- Each valve 442A, 442B includes a delivery line 443A, 443B having a valve seat assembly 444A, 444B and includes a purge line 445A, 445B having a valve seat assembly 446A, 446B in fluid with valves 452A, 452B.
- the delivery line 443A, 443B is in communication with the reactant gas source 438, 439 and is in communication with the gas inlet 436A, 436B of the expanding channel
- Additional reactant gas sources e.g., WVG system output
- delivery lines e.g., gas inlets and valves
- valves may be added to the gas delivery apparatus 430 in one embodiment (not shown).
- 443A, 443B controls the flow of the reactant gas from the reactant gas source 438,
- the purge line 445A, 445B is in communication with the purge gas source 440 and intersects the delivery line 443A, 443B downstream of the valve seat assembly 444A, 444B of the delivery line 443A, 443B.
- the valve seat assembly 446A, 446B of the purge line 4745A, 445B controls the flow of the purge gas from the purge gas source 440 to the delivery line 443A, 443B.
- a carrier gas is used to deliver reactant gases from the reactant gas source 438, 439, preferably the same gas is used as a carrier gas and a purge gas (e.g., nitrogen used as a carrier gas and a purge gas).
- reactant gas source 438 contains TDMAS or Tris-DMAS and gas source 439 contains an oxidizing gas containing water vapor from a WVG system.
- Gas source 439 may be in fluid communication with a WVG system or.
- gas source 439 may be a WVG system.
- Each valve seat assembly 444A, 444B, 446A, 446B may comprise a diaphragm and a valve seat.
- the diaphragm may be biased open or closed and may be actuated closed or open respectively.
- the diaphragms may be pneumatically actuated or may be electrically actuated. Examples of pneumatically actuated valves include pneumatically actuated valves available from Fujiken and Veriflow. Examples of electrically actuated valves include electrically actuated valves available from Fujiken.
- Programmable logic controllers 448A, 448B may be coupled to the valves 442A, 442B to control actuation of the diaphragms of the valve seat assemblies 4744A, 444B, 446A, 446B of the valves 442A, 442B.
- Pneumatically actuated valves may provide pulses of gases in time periods as low as about 0.020 seconds.
- Electrically actuated valves may provide pulses of gases in time periods as low as about 0.005 seconds.
- An electrically actuated valve typically requires the use of a driver coupled between the valve and the programmable logic controller.
- Each valve 442A, 442B may be a zero dead volume valve to enable flushing of a reactant gas from the delivery line 443A, 443B when the valve seat assembly 444A, 444B of the valve is closed.
- the purge line 445A, 445B may provide a purge gas to flush the delivery line 443A,
- a zero dead volume valve as used herein is defined as a valve which has negligible dead volume (i.e., not necessary zero dead volume.)
- Each valve 442A, 442B may be adapted to provide a combined gas flow and/or separate gas flows of the reactant gas 438, 439 and the purge gas 440.
- a combined gas flow of the reactant gas 438 and the purge gas 440 provided by valve 442A comprises a continuous flow of a purge gas from the purge gas source 440 through purge line 445A and pulses of a reactant gas from the reactant gas source 438 through delivery line 443A.
- the continuous flow of the purge gas may be provided by leaving diaphragm of the valve seat assembly 446A of the purge line 445A open.
- the pulses of the reactant gas from the reactant gas source 438 may be provided by opening and closing the diaphragm of the valve seat 444A of the delivery line 443A.
- one example of separate gas flows of the reactant gas 438 and the purge gas 440 provided by valve 442A comprises pulses of a purge gas from the purge gas source 440 through purge line 445A and pulses of a reactant gas from the reactant gas source 438 through delivery line 443A.
- the pulses of the purge gas may be provided by opening and closing the diaphragm of the valve seat assembly 446A of the purge line 445A open.
- the pulses of the reactant gas from the reactant gas source 438 may be provided by opening and closing the diaphragm valve seat 444A of the delivery line 443A.
- the delivery lines 443A, 443B of the valves 442A, 442B may be coupled to the gas inlets 436A, 436B through gas conduits 450A, 450B.
- the gas conduits 450A, 450B may be integrated or may be separate from the valves 442A, 442B.
- the valves 442A, 442B are coupled in close proximity to the expanding channel 434 to reduce any unnecessary volume of the delivery line 443A, 443B and the gas conduits 450A, 450B between the valves 442A, 442B and the gas inlets 436A, 436B.
- the expanding channel 434 comprises a channel which has an inner diameter which increases from an upper portion 437 to a lower portion 435 of the expanding channel 434 adjacent the bottom surface 460 of the chamber lid 432.
- the inner diameter of the expanding channel 434 for a chamber adapted to process 200 mm diameter substrates is between about 0.2 inches (0.51 cm) and about 1.0 inches (2.54 cm), preferably between about 0.3 inches (0.76 cm) and about 0.9 inches (2.29 cm) and more preferably between about 0.3 inches (0.76 cm) and about 0.5 inches (1.27 cm) at the upper portion 437 of the expanding channel 434 and between about 0.5 inches (1.27 cm) and about 3.0 inches (7.62 cm), preferably between about 0.75 inches (1.91 cm) and about 2.5 inches (6.35 cm) and more preferably between about 1.1 inches (2.79 cm) and about 2.0 inches (5.08 cm) at the lower portion 435 of the expanding channel 434.
- the inner diameter of the expanding channel 434 for a chamber adapted to process 300 mm diameter substrates is between about 0.2 inches (0.51 cm) and about 1.0 inches (2.54 cm), preferably between about 0.3 inches (0.76 cm) and about 0.9 inches (2.29 cm) and more preferably between about 0.3 inches (0.76 cm) and about 0.5 inches (1.27 cm) at the upper portion 437 of the expanding channel 434 and between about 0.5 inches (1.27 cm) and about 3.0 inches (7.62 cm), preferably between about 0.75 inches (1.91 cm) and about 2.5 inches (6.35 cm) and more preferably between about 1.2 inches (3.05 cm) and about 2.2 inches (5.59 cm) at the lower portion 435 of the expanding channel 434 for a 300 mm substrate.
- the above dimension apply to an expanding channel adapted to provide a total gas flow of between about 500 seem and about 3,000 seem.
- the dimension may be altered to accommodate a certain gas flow therethrough.
- a larger gas flow will require a larger diameter expanding channel.
- the expanding channel 434 may be shaped as a truncated cone (including shapes resembling a truncated cone). Whether a gas is provided toward the walls of the expanding channel 434 or directly downward towards the substrate, the velocity of the gas flow decreases as the gas flow travels through the expanding channel 434 due to the expansion of the gas. The reduction of the velocity of the gas flow helps reduce the likelihood the gas flow will blow off reactants adsorbed on the surface of the substrate 390.
- the diameter of the expanding channel 434 which is gradually increasing from the upper portion 437 to the lower portion 435 of the expanding channel, allows less of an adiabatic expansion of a gas through the expanding channel 434 which helps to control the temperature of the gas.
- a sudden adiabatic expansion of a gas delivered through the gas inlet 436A, 436B into the expanding channel 434 may result in a drop in the temperature of the gas which may cause condensation of the precursor vapor and formation of particles.
- a gradually expanding channel 434 according to embodiments of the present invention is believed to provide less of an adiabatic expansion of a gas.
- the gradually expanding channel may comprise one or more tapered inner surfaces, such as a tapered straight surface, a concave surface, a convex surface, or combinations thereof or may comprise sections of one or more tapered inner surfaces (i.e., a portion tapered and a portion non-tapered).
- the gas inlets 436A, 436B are located adjacent the upper portion 437 of the expanding channel 434. In other embodiments, one or more gas inlets may be located along the length of the expanding channel 434 between the upper portion 437 and the lower portion 435.
- a control unit 480 such as a programmed personal computer, work station computer, or the like, may be coupled to the process chamber 380 to control processing conditions.
- the control unit 480 may be configured to control flow of various process gases and purge gases from gas sources 438, 439, 440 through the valves 442A, 442B during different stages of a substrate process sequence.
- the control unit 480 comprises a central processing unit (CPU) 482, support circuitry 484, and memory 486 containing associated control software 483.
- the control unit 480 may be one of any form of general purpose computer processor that can be used in an industrial setting for controlling various chambers and sub-processors.
- the CPU 482 may use any suitable memory 486, such as random access memory, read only memory, floppy disk drive, compact disc drive, hard disk, or any other form of digital storage, local or remote.
- Various support circuits may be coupled to the CPU 482 for supporting the process chamber 380.
- the control unit 480 may be coupled to another controller that is located adjacent individual chamber components, such as the programmable logic controllers 448A, 448B of the valves 442A, 442B.
- Bi-directional communications between the control unit 480 and various other components of the process chamber 380 are handled through numerous signal cables collectively referred to as signal buses 488, some of which are illustrated in Figure 4.
- the control unit 480 may be configured to be responsible for automated control of other activities used in wafer processing, such as wafer transport, temperature control, chamber evacuation, among other activities, some of which are described elsewhere herein.
- a "substrate surface,” as used herein, refers to any substrate or material surface formed on a substrate upon which a process may be performed.
- a substrate surface on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application.
- Barrier layers, metals or metal nitrides on a substrate surface include titanium, titanium nitride, tungsten nitride, tantalum and tantalum nitride.
- Substrates may have various dimensions, such as 200 mm or 300 mm diameter wafers, as well as, rectangular or square panes. Processes of the embodiments described herein deposit silicon- containing layers on many substrates and surfaces, especially, high-k dielectric materials. Substrates on which embodiments of the invention may be useful include, but are not limited to semiconductor wafers, such as crystalline silicon (e.g., Si ⁇ 100> or Si ⁇ 111 >), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or non- patterned wafers. Substrates may be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal and/or bake the substrate surface.
- semiconductor wafers such as crystalline silicon (e.g., Si ⁇ 100> or Si ⁇ 111 >), silicon oxide, strained silicon, silicon germanium, doped or undoped polysilicon, doped or undoped silicon wafers and patterned
- Atomic layer deposition or “cyclical deposition” as used herein refers to the sequential introduction of two or more reactive compounds to deposit a layer of material on a substrate surface.
- the two, three or more reactive compounds may alternatively be introduced into a reaction zone of a process chamber.
- each reactive compound is separated by a time delay to allow each compound to adhere and/or react on the substrate surface.
- a first precursor or compound A is pulsed into the reaction zone followed by a first time delay.
- a second precursor or compound B is pulsed into the reaction zone followed by a second delay.
- a purge gas such as nitrogen
- the purge gas may flow continuously throughout the deposition process so that only the purge gas flows during the time delay between pulses of reactive compounds.
- the reactive compounds are alternatively pulsed until a desired film or film thickness is formed on the substrate surface.
- the ALD process of pulsing compound A, purge gas, pulsing compound B and purge gas is a cycle.
- a cycle can start with either compound A or compound B and continue the respective order of the cycle until achieving a film with the desired thickness.
- a first precursor containing compound A, a second precursor containing compound B and a third precursor containing compound C are each separately pulsed into the process chamber.
- a pulse of a first precursor may overlap in time with a pulse of a second precursor while a pulse of a third precursor does not overlap in time with either pulse of the first and second precursors.
- a "pulse" as used herein is intended to refer to a quantity of a particular compound that is intermittently or non-continuously introduced into a reaction zone of a processing chamber. The quantity of a particular compound within each pulse may vary over time, depending on the duration of the pulse.
- each pulse is variable depending upon a number of factors such as, for example, the volume capacity of the process chamber employed, the vacuum system coupled thereto, and the volatility/reactivity of the particular compound itself.
- the ALD processes are maintained at a temperature in a range from about 70°C to about 1 ,000°C, preferably from about 100°C to about 400°C, for example, about 250°C.
- the ALD processes are conducted in a process chamber at a pressure within the range from about 0.1 Torr to about 100 Torr, preferably from about 1 Torr to about 10 Torr.
- Carrier gas e.g., N 2 or Ar
- Example 1 - A silicon-containing capping layer is formed on a high-k gate dielectric. Initially, a substrate is placed in to an ALD chamber and the substrate surface is exposed to a pretreatment of water vapor to form hydroxyl groups. A hafnium silicate layer is deposited to the substrate surface by performing an ALD process using the hafnium precursor (TDEAH), the silicon precursor (TDMAS), and in-situ water vapor produced by a water vapor generator (WVG) system, available from Fujikin of America, Inc., located in Santa Clara, California.
- the ALD cycle includes sequentially pulsing TDEAH, water vapor, TDMAS and water vapor, with each precursor separated by a nitrogen purge.
- the hafnium silicate layer is formed by repeating the cycle until the film has a thickness of about 100 A.
- the silicon-containing capping layer is formed on the hafnium silicate layer in the same ALD chamber.
- Silicon oxide is grown with an ALD process by sequentially pulsing a silicon precursor (TDMAS) with in-situ water vapor formed from a WVG system.
- Carrier gas such as nitrogen, is directed into the ALD process chamber with a flow rate of about 2 slm.
- the TDMAS is dosed into the carrier gas and pulsed into the chamber for about 1 second.
- a purge gas of nitrogen is pulsed into the chamber for 1.5 seconds to remove any unbound TDMAS.
- Hydrogen gas and oxygen gas with the flow rate of 100 seem and 80 seem respectively, are supplied the WVG system.
- the in-situ water vapor is pulsed into the chamber for 1.7 seconds.
- the purge gas of nitrogen is pulsed into the chamber for 1.5 seconds to remove any unbound or non-reacted reagents.
- the ALD cycle is repeated 8 times to produce a silicon oxide layer with a thickness of about 5 A.
- the substrate is transferred to a decoupled plasma nitridation (DPN) chamber, such as the CENTURATM DPN chamber, available from Applied Materials, Inc., located in Santa Clara, California.
- DPN decoupled plasma nitridation
- the substrate surface is exposed to a nitridation process by co-flowing N 2 with an argon plasma.
- the nitridation process proceeds for about 30 seconds to incorporate nitrogen atoms within the silicon oxide layer.
- the substrate is subsequently transferred to an annealing chamber, such as the CENTURATM RADIANCETM RTP chamber available from Applied Materials, Inc., located in Santa Clara, California and exposed to an annealing process.
- the substrate is maintained at about 1 ,000°C for about 1 minute in an O 2 atmosphere maintained at about 15 Torr.
- the incorporated nitrogen atoms form bonds with the silicon oxide to produce silicon oxynitride.
- Example 2 A silicon-containing capping layer is formed on a high-k gate dielectric. Initially, a substrate is placed in to an ALD chamber equipped with a remote plasma generator and the substrate surface is exposed to a pretreatment of water vapor to form hydroxyl groups. A hafnium silicate layer is deposited to the substrate surface by performing an ALD process using the hafnium precursor (HfCI ), the silicon precursor (Tris-DMAS), and in-situ water vapor produced by a WVG system. The ALD cycle includes sequentially pulsing HfCI 4 , water vapor, Tris- DMAS and water vapor, with each precursor separated by an argon purge.
- HfCI hafnium precursor
- Tris-DMAS silicon precursor
- Water vapor Tris- DMAS
- the hafnium silicate layer is formed by repeating the cycle until the film has a thickness of about 50 A, subsequently, the ALD cycle is altered.
- the hafnium precursor pulses and one of the water vapor pulses are stopped. Therefore, the ALD cycle, forming silicon oxide instead of hafnium silicate, includes continuing sequential pulsing of Tris-DMAS and water vapor formed by the WVG system.
- Carrier gas such as argon, is directed into the ALD process chamber with a flow rate of about 2 slm.
- the Tris-DMAS is dosed into the carrier gas and pulsed into the chamber for about 1 second.
- a purge gas of argon is pulsed into the chamber for 1.5 seconds to remove any unbound Tris-DMAS.
- Hydrogen gas and oxygen gas with the flow rate of 100 seem and 80 seem respectively, are supplied the WVG system.
- the in-situ water vapor exits from the WVG system with approximately 100 seem of water and about 30 seem of oxygen.
- the in-situ water vapor is pulsed into the chamber for 1.7 seconds.
- the argon purge gas is pulsed into the chamber for 1.5 seconds to remove any unbound or non-reacted reagents.
- the ALD cycle is repeated 8 times to produce a silicon oxide layer with a thickness of about 5 A.
- the substrate is kept in the same ALD chamber equipped with a remote plasma generator.
- the substrate surface is exposed to a remote plasma nitridation process for about 30 seconds to incorporate nitrogen atoms within the silicon oxide layer.
- the substrate is subsequently transferred to an annealing chamber, such as the CENTURATM RADIANCETM RTP chamber available from Applied Materials, Inc., located in Santa Clara, California and exposed to an annealing process.
- the substrate is maintained at about 1 ,000°C for about 1 minute in an O 2 atmosphere maintained at about 15 Torr.
- the incorporated nitrogen atoms form bonds with the silicon oxide to produce silicon oxynitride.
Abstract
Description
Claims
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JP2007527310A JP2008500742A (en) | 2004-05-21 | 2005-05-12 | Formation of silicon oxynitride layers on high dielectric constant dielectric materials |
EP05749300A EP1747581A1 (en) | 2004-05-21 | 2005-05-12 | Formation of a silicon oxynitride layer on a high-k dielectric material |
CN2005800061381A CN1926668B (en) | 2004-05-21 | 2005-05-12 | Formation of a silicon oxynitride layer on a high-K dielectric material |
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Also Published As
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US20050260347A1 (en) | 2005-11-24 |
JP2008500742A (en) | 2008-01-10 |
CN1926668B (en) | 2010-09-01 |
EP1747581A1 (en) | 2007-01-31 |
US8119210B2 (en) | 2012-02-21 |
CN1926668A (en) | 2007-03-07 |
KR20070013337A (en) | 2007-01-30 |
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