WO1997047783A1 - Methodologie et appareil de dopage local de revetements en aluminium - Google Patents

Methodologie et appareil de dopage local de revetements en aluminium Download PDF

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Publication number
WO1997047783A1
WO1997047783A1 PCT/US1997/010435 US9710435W WO9747783A1 WO 1997047783 A1 WO1997047783 A1 WO 1997047783A1 US 9710435 W US9710435 W US 9710435W WO 9747783 A1 WO9747783 A1 WO 9747783A1
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aluminum
plasma
copper
substrate
group
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PCT/US1997/010435
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English (en)
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Alain E. Kaloyeros
Andreas Knorr
Jonathan Faltermeier
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The Research Foundation Of State University Of New York
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Publication of WO1997047783A1 publication Critical patent/WO1997047783A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/44—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 method of coating
    • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/44—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 method of coating
    • C23C16/50—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 method of coating using electric discharges
    • C23C16/505—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 method of coating using electric discharges using radio frequency discharges
    • C23C16/509—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 method of coating using electric discharges using radio frequency discharges using internal electrodes
    • C23C16/5096—Flat-bed apparatus

Definitions

  • the present invention relates to conformal doped aluminum coatings on a patterned substrate and a methodology and apparatus to prepare such doped coatings. More particularly, the present invention is directed to the controlled, reproducible growth by thermal or plasma-assisted CVD (PACVD) processes of ultrathin Cu layers which are subsequently used as seed surface for the in-situ thermal or PACVD formation of smooth, copper-doped aluminum films which conformally coat semiconductor device substrates with patterned holes, vias, and trenches with aggressive aspect ratios (hole depth/hole width ratios).
  • PSVD thermal or plasma-assisted CVD
  • Al alloys As the main building block of the IC interconnects, Al alloys have played a major role in the evolution of the computer age. When alloyed with 0.5 wt% copper, Al exhibits enhanced electromigration resistance while maintaining good electrical conductivity. In addition to its ability for self passivation in air and ease of patternability in chlorine based plasmas, Al bonds well to SiO 2 and diffusion barriers of titanium nitride and titanium. See S.P. Murarka, Metallization; Theory and Practice for VLSI and VLSI ⁇ Butterworth-Heinemann, Boston, 1993). In light of these properties, Al based metallizations are predicted not only to continue as the interconnection workhorse of the integrated circuit industry in the foreseeable future, but will extend their role in providing contact and via hole plugs for all wiring levels.
  • Chemical vapor deposition (CVD) of Al presents a viable alternative to PVD due to its inherent ability to grow films conformally on via and trench structures.
  • Efforts to develop CVD Al deposition techniques date as far back as the late 1940's, wherein a variety of chemical sources were used which included Al halide, alkyl, and organometallic sources. See, for example, C.F. Powell, J.H. Oxley, and J.M. Blocher, Jr., Vapor Deposition ⁇ Wiley, New York, New York, 1966) p. 27; and H.J. Cooke, R.A. Heinecke, R.C. Stem, and J. W.C. Maas, Solid State Technol. 25 (1982) 62.
  • the Cu doped Al films must be of especially ultra high quality, in terms of purity, with impurity concentrations well below 1 atomic percent, must exhibit excellent electromigration properties, must be highly specular, with extremely smooth surface morphology, and must be conformal to the complex topography of ULSI circuitry to provide complete filling of aggressive via and trench structures.
  • Recent work has successfully produced aluminum films doped with 0.7-1.4 wt% copper through the simultaneous decomposition in the same CVD reactor of dimethylaluminum hydride (DMAH) and cyclopentadienyl copper triethylphosphine which were employed, respectively, as the aluminum and copper sources.
  • DMAH dimethylaluminum hydride
  • cyclopentadienyl copper triethylphosphine which were employed, respectively, as the aluminum and copper sources.
  • a process which can control the deposition of the Cu layers down to extremely low thicknesses, e.g., below 20A.
  • This feature is required to ensure that, upon annealing or mixing with aluminum, copper concentration in the doped aluminum film does not exceed 0.5 wt%.
  • This upper limit is needed to prevent any problems in the subsequent Al interconnect etching and patterning steps, although recent technological advances in these areas could eventually push that number to values as high as 3 to 5 wt%.
  • the process must allow deposition of a bilayered stack consisting of an ultrathin Cu layer followed by Al. The latter is particularly desired because copper is known to inhibit undesirable aluminum grain growth through alloying.
  • copper's use as growth surface in aluminum CVD provides a good seed layer for the uniform nucleation of aluminum grains, leading to smaller grain size and significantly smoother morphology, as desired in microelectronics applications.
  • the process must be flexible to allow use of thermal CVD processing for ultrathin copper films in combination with plasma assisted CVD of aluminum or vice versa.
  • PVD techniques such as sputtering, reflow, plating, or electroplating, in combination with, or in lieu of, the CVD approaches described above to deposit one or both metallic layers.
  • substrate bias could be applied to the substrate during either deposition step. The purpose is to form a "soft" plasma region above the substrate to assist in the actual decomposition process, and/or attract ionized aluminum or copper ions to the various topographical regions of the substrate, leading to more conformal via and trench filling.
  • the invention includes a method and apparatus for the chemical vapor deposition of conformal copper-doped aluminum layers on substrates.
  • the invention deposits copper-doped aluminum metallization layers on semiconductor Substrates, such as silicon and gallium arsenide.
  • the invention deposits the two metals in-situ, sequentially, with ultrathin copper layer being deposited first and used as seed layer in the deposition of smooth, aluminum films with the grain size and texture required for microelectronics applications.
  • sequentially deposited copper-aluminum layers are annealed in-situ or ex-situ to form a copper doped aginanum film.
  • the Cu, Al, and in-situ annealing could take place either in the same reactor, in two separate reactors, one used for deposition and the other for annealing, or in three separate reactors. In the cases when more than one reactor is used, it is preferred that the reactors be inter-connected through leak-tight transfer arms/load locks. The transfer arms/load locks allow sample transfer between the different reactors without exposure to air. Alternatively, the invention provides for depositing the aluminum film on the copper seed layer at a temperature sufficient to form a smooth, copper-doped, aluminum film without the need for the annealing step.
  • the invention provides a means to accurately and repeatably transport copper precursor gas to the reaction zone at a rate and flux which allow reproducible deposition of ultrathin copper layers, e.g., as thin as 10-15A, within 1-2A accuracy.
  • the invention uses copper source precursors which have been diluted in a precursor carrier medium at significantly reduced precursor concentration levels.
  • any suitable copper precursor can be used, regardless of whether it is a solid, liquid or gas.
  • the precursor carrier medium could include solvents, water, or an adducted form of the source precursor.
  • the mixture of copper precursor and associated medium can be vaporized prior to its introduction to the reaction zone, or inside the reaction zone.
  • the precursor carrier medium could include inert gases such as nitrogen, argon, xenon, or helium, or more active gases such as hydrogen.
  • the invention uses highly diluted precursor concentrations to enable tight control over precursor transport and delivery rates, and to ensure the delivery of very low fluxes of copper precursor gas to the reaction zone.
  • any precursor delivery system including pressure-based bubblers, liquid delivery systems, direct liquid injection systems, standard and hot source mass flow controllers, can be used to deliver the mixtures of precursor and carrier medium to the reaction zone.
  • the invention also provides a heat assisted chemical vapor deposition process and apparatus.
  • copper then aluminum are deposited sequentially on the substrate.
  • This process is carried out using copper and aluminum precursor gases in combination with the precursor transport means discussed above.
  • the aluminum precursors could be solid, liquid, or gaseous at room temperature, and could be heated to transform them into a gas which is easily transportable to the reactor.
  • the precursors gases are reacted with suitable reactant gases such as hydrogen, argon, nitrogen, or a mixture thereof. The reaction takes place in a reactor under conditions ranging from one atmosphere to high vacuum and at temperatures less than 650°C.
  • the invention also provides for plasma, light, or laser assisted chemical vapor deposition. It uses the energy provided by the plasma, light, or laser to deposit either the copper or aluminum layer, or both.
  • an electrical bias could be applied to the substrate at power densities ranging from 0.005 W/cm 2 to 100 W/CM 2 and frequencies ranging from 1 Hz to 10 8 kHz.
  • the local electrical field in the region above and at the surface of the substrate enhances the rate of impingement of copper and aluminum ions from the copper and aluminum precursor gases, leading to more conformal coating of the topographies of microelectronics device structures.
  • FIG. I is a diagrammatic representation of the reaction apparatus used to achieve chemical vapor deposition and plasma assisted chemical vapor deposition according to the present invention.
  • FIG. 2 is a Rutherford backscattering (RBS) spectrum of a bilayered stack consisting of a thermal CVD grown, 380 ⁇ A-thick, Al film deposited in-situ on a PACVD grown copper seed layer, prior to annealing to form the doped aluminum phase.
  • RBS Rutherford backscattering
  • FIG. 3 is a Rutherford backscattering (RBS) spectrum of the same sample shown in FIG. 2 after annealing for 100 minutes at 450°C in one atmosphere of hydrogen.
  • the RBS spectrum indicates an Al phase doped with 0.8 at%Cu (Al-2.0 wt% Cu), with the copper being distributed uniformly throughout the Al matrix. No impurities or contaminants, such as oxygen, carbon, or fluorine were observed in the doped aluminum film.
  • FIG. 4 is an atomic force microscopy (AFM) micrograph of a 380 ⁇ A-thick copper- doped aluminum film grown according to the process of the present invention. AFM indicates a smooth surface morphology with small aluminum grains.
  • AFM atomic force microscopy
  • FIG. 5 is an atomic force microscopy (AFM) micrograph of a 720 ⁇ A-thick aluminum film grown by thermal CVD without a copper seed layer. AFM indicates a rough surface morphology with extremely large aluminum grains.
  • FIG. 6 is an Auger electron spectroscopy (AES) spectrum of an Al-Cu stack after annealing for 100 minutes at 450°C in one atmosphere of hydrogen.
  • the stack consisted of a thermal CVD grown, 8000 A-thick, Al film deposited in-situ on a PACVD grown copper seed layer.
  • the RBS spectrum indicates an Al phase doped with 3 at%Cu (Al-7.5 wt% Cu), with the copper being distributed uniformly throughout the Al matrix. No impurities or contaminants, such as oxygen, carbon, or fluorine were observed in the doped aluminum film.
  • FIG. 7 is an atomic force microscopy (AFM) micrograph of an 800 ⁇ A-thick copper- doped aluminum film grown according to the process of the present invention. AFM indicates a smooth surface mo ⁇ hology with small aluminum grains.
  • FIG. 8 is a Rutherford backscattering (RBS) spectrum of an Al-Cu stack after annealing for 100 minutes at 450°C in one atmosphere of hydrogen.
  • the stack consisted of PACVD deposited Al-Cu-Al trilayer stack.
  • the RBS spectrum indicates an Al phase doped with 0.1 at%Cu (Al-2.5 wt% Cu), with the copper being distributed uniformly throughout the Al matrix. No impurities or contaminants, such as oxygen, carbon, or fluorine were observed in the doped aluminum film.
  • FIG. 8 is a Rutherford backscattering (RBS) spectrum of an Al-Cu stack after annealing for 100 minutes at 450°C in one atmosphere of hydrogen.
  • the stack consisted of PACVD deposited Al-Cu-Al trilayer stack.
  • the RBS spectrum indicates an Al phase doped with 0.1 at%Cu (Al-2.5 wt% Cu), with the copper being distributed uniformly throughout the Al matrix. No impurities or contaminants, such as oxygen
  • FIG. 9 depicts cross sections, magnified by scanning electron microscopy, of semiconductor cantilever structures consisting of silicon substrates upon which "overhang" silicon oxide patterns are formed and upon which copper and aluminum layers were deposited by CVD and PACVD.
  • aluminum was deposited directly on the overhang structure by conventional CVD without using the copper seed layer.
  • the present invention was applied to grow an Al-Cu stack consisting of approximately 1 ⁇ m-thick Al film on an ultrathin copper seed layer.
  • a comparison of the two cross sections demonstrates how the ultrathin copper seed layer inhibits undesirable large aluminum grain growth, yielding the texture and composition required for microelectronics applications.
  • FIG. 10 depicts cross sections, magnified by scanning electron microscopy, of cantilever structures similar to the ones shown in FIG. 9. Copper and aluminum layers were deposited on these structures by CVD and PACVD under conditions identical to those used for FIG. 9, except for aluminum precursor flow which was three times higher in this case.
  • aluminum was deposited directly on the overhang structure by conventional CVD without using the copper seed layer.
  • the present invention was applied to grow an Al-Cu stack consisting of approximately 1 ⁇ m-thick Al film on an ultrathin copper seed layer.
  • a comparison of the two cross sections demonstrates how the ultrathin copper seed layer inhibits undesirable large aluminum grain growth, yielding the texture and composition required for microelectronics applications.
  • FIG. 10 depicts cross sections, magnified by scanning electron microscopy, of cantilever structures similar to the ones shown in FIG. 9. Copper and aluminum layers were deposited on these structures by CVD and PACVD under conditions identical to those used for FIG. 9, except for aluminum precursor flow which was three times higher in this case.
  • aluminum was
  • FIG. 1 1 is a plot of the RBS spectra of two ultrathin Cu layers grown by PACVD on Si substrates using the delivery approach of the present invention.
  • the RBS data shows a highly repeatable Cu thickness of 8 ⁇ A.
  • FIG. 12 is a plot of the RBS spectra of two ultrathin (8 ⁇ A) Cu layers grown by PACVD on TiN substrates using the delivery approach of the present invention.
  • the RBS data shows a highly repeatable Cu thickness of 8 ⁇ A.
  • the invention includes CVD-based processes that prepare copper-doped aluminum films which are suitable as signal conductors (both plug and interconnect) in integrated circuit fabrication, and in particular in ULSI computer device fabrication and beyond.
  • the process of the invention directs carefully selected precursors to a thermal or plasma assisted CVD reactor, under carefully specified reaction conditions, for the in-situ deposition of ultrathin copper layers which are subsequently used as seed layer in the deposition of smooth copper-doped aluminum films with the grain size and texture required for microelectronics applications.
  • sequentially deposited copper-aluminum layers are annealed in-situ or ex-situ to form a copper doped aluminum film.
  • the aluminum film is deposited on the copper seed layer at a temperature sufficient to form a smooth, c ⁇ pper-doped, aluminum film without the need for the annealing step.
  • the term "aluminum film” is used to refer to a film made from pure aluminum metal.
  • the term “doped aluminum film” is used to refer to a film made from blends of aluminum metal and a second metal which is selected from Groups lb, lib and Vlllb of the Periodic Table, such as copper.
  • the term “bilayered aluminum film” refers to bilayers formed from any of aluminum metal, copper metal and blends thereof, which are either deposited in-situ in at a temperature sufficient to form a copper-doped aluminum film without the need for the annealing step, or are subsequently annealed to yield an aluminum-copper alloy.
  • the formation of copper or aluminum films is achieved by using plasma assisted CVD (PACVD), which refers to a CVD process wherein all reactants are introduced to the CVD reactor in gaseous form, and the energy necessary for bond cleavage is supplied partially by the high energy electrons formed in glow discharges or plasmas of light ions (primarily hydrogen or helium) with low plasma power densities (below 0.25 W/cm 2 ).
  • plasma assisted CVD PECVD
  • the use of low power densities in PACVD prevents undesirable precursor decomposition in the gas phase, thus minimizing the potential for precursor decomposition in the gas phase and film contamination, and jjihibiting electrical damage to film and substrate.
  • the use of light ions (hydrogen or helium) in PACVD prevents mechanical and structural damage to film and substrate, which results from the impingement of heavy ions such as argon in PECVD.
  • the plasma is generated through use of radio frequency (RF) glow discharges, although plasmas with frequencies ranging from kHz to GHz could be employed. See, generally, Hess, D. W. and Graves, D.
  • the formation of copper or aluminum films is achieved by using plasma processing, including PECVD, or PACVD in combination with substrate bias.
  • plasma processing including PECVD, or PACVD in combination with substrate bias.
  • substrate bias leads to a significant enhancement in the flux of metal ions impinging on the substrate and a corresponding increase in the re- emission probability of such atoms inside via and trench structures.
  • These re-emission processes are known to create improved step coverage in patterned holes, vias, and trenches with aggressive aspect ratios (0.25 ⁇ M features with 4 to 1 aspect ratios and beyond).
  • the present invention can be used with any CVD reactor which has the following basic components: a precursor delivery system which is used to store and control the delivery of the source precursor, a vacuum chamber and pumping system to maintain an appropriately reduced pressure; a wafer and reactor temperature control system, and gas or vapor handling capabilities to meter and control the flow of reactants and products that result from the process. Additional features that are needed to implement specific embodiments of the present invention include a power supply to create the discharge and/or a power supply to apply a bias to the substrate. According to one preferred embodiment for the deposition of doped Al films, the CVD reactor shown in Fig. 1 was employed.
  • the copper source precursor 10 is placed in the reservoir (bubbler/sublimator) 11 which could be heated by a combination resistance heating tape and associated power supply 12 to a temperature which is high enough to ensure the sublimation or vaporization of the copper source, but not too high to cause its premature decomposition.
  • a mass flow controller 13 which can be isolated from the bubbler by a high vacuum valve 14, is used to control the flow of gas (hydrogen, argon, xenon, or nitrogen) into the reservoir through inlet 15. This gas serves as carrier agent when a conventional pressure and/or temperature based mass flow control type delivery system 11 and 13 is employed to control the flow of precursor into the CVD reactor 17.
  • the gas serves as a pressurizing agent when a liquid delivery system 16, consisting of a combination micropump and vaporizer head, such as the MKS Direct Liquid Injection (DLI) system, is applied to the delivery of the precursor to the CVD reactor 17.
  • a hot source mass flow controller 16 such as an MKS Model 1 150 MFC, which does not require the use of a carrier or pressurizing gas.
  • the delivery system is isolated from the precursor reservoir by a high vacuum valve 18, and the precursor vapor or (precursor + carrier gas) mixture vapors is then transported through a high vacuum isolation valve 19 and a cone-shaped shower head
  • the shower head 20 is employed to ensure proper reactant mixing and uniformity in reactant delivery and flow over 8" wafers.
  • the cone was 18" high, and was designed with Conflat type top and bottom fittings.
  • the bottom opening (towards the reactor) was 7", while the top opening was 1.3". It should be noted, however, that other commercially available shower head designs are equally effective at providing the reactant mixing capabilities and uniformity required.
  • All transport and delivery lines and high vacuum isolation valves 18, 19, and 20 are maintained at the precursor sublimation/vaporization temperature, using typical combinations of resistance heating tapes and associated power supplies 21 and 22, to prevent precursor recondensation.
  • the reactor 17 is an 8" wafer, cold wall stainless steel CVD reactor. It is equipped with a parallel plate type plasma configuration made of two electrodes 26 and 27, with the reactor itself providing electrical grounding.
  • the upper plate 26 serves as the active discharge electrode and is driven by a plasma generator 28, such as a radio frequency (13.56 MHz) power supply.
  • This upper plate is constructed in a "mesh" type pattern to allow unconstricted reactant flow to the substrate 29.
  • a hydrogen plasma is used for in-situ predeposition substrate cleaning at plasma power densities in the range 0.1- 0.25 W/cm 2 .
  • a mass flow controller 23 which can be isolated from the bubbler by a high vacuum valve 24, is used to ensure delivery of additional hydrogen, argon, or nitrogen flow to the reactor through the side feedthrough 25.
  • the substrate (wafer) 29 is placed on the lower electrode 27, and is heated to processing temperatures in the range 70-450°C by an 8" resistive heater 30.
  • the lower plate also serves as the bias electrode and could be driven by a frequency generator 31, such as a low frequency (95-450 kHz) power supply, when, according to some preferred embodiments, thermal or plasma promoted CVD with biased substrate are used.
  • the reactor is periodically baked under a nitrogen or argon atmosphere to below 0.3 Torr and then pumped down to below IO "7 Torr for an hour at, 150°C.
  • the pumping stack 32 consists of two pumping packages, the first cryogenic or turbomolecular pump based, and the second roots blower pump based, and is isolated from the reactor high conductance pumping lines 33 by the high vacuum gate valve 34.
  • the cryogenic pump based package is used to ensure high vacuum base pressure in the reactor, while the roots blower based package is employed for appropriate handling of the high gas throughput during actual CVD runs.
  • a high vacuum load lock system is typically used for transport and loading of 8" wafers into the reactor.
  • the aluminum source precursor 35 is placed in the reservoir (bubbler/sublimator) 36 which could be heated by a combination resistance heating tape and associated power supply 37 to a temperature which is high enough to ensure the sublimation or vaporization of the aluminum source, but not too high to cause- its premature decomposition.
  • a mass flow controller 38 which can be isolated from the bubbler by a high vacuum valve 39, is used to control the flow of gas (hydrogen argon, xenon, or nitrogen) into the reservoir through inlet 40. This gas serves as carrier agent when a conventional pressure or temperature based mass flow control type delivery system 36 and 38 is employed to control the flow of precursor into the CVD reactor 17.
  • the gas serves as a pressurizing agent when a liquid delivery system 41, consisting of a combination micropump and vaporizer head, such as the MKS Direct Liquid Injection (DLI) system, is applied to the delivery of the precursor to the CVD reactor 17.
  • a liquid delivery system 41 consisting of a combination micropump and vaporizer head, such as the MKS Direct Liquid Injection (DLI) system
  • DLI Direct Liquid Injection
  • a third possibility is to use a hot source mass flow controller 41, such as an
  • the delivery system is isolated from the precursor reservoir by a high vacuum valve 42, and the precursor vapor or (precursor + carrier gas) mixture vapors is then transported through a high vacuum isolation valve 19 and a cone-shaped shower head 20 into the CVD reactor 17. All transport and delivery lines and high vacuum isolation valves 39, 40, and 42, are maintained at the aluminum precursor sublimation/vaporization temperature, using a typical combination of resistance heating tape and associated power supply 43, to prevent precursor recondensation.
  • ⁇ IOO A ultrathin
  • the formation of the copper seed layer, wherein an ultrathin layer is needed can be controlled reproducibly from run to run through using an appropriately composed flux of source copper precursor. This is achieved by employing mixtures of copper source precursors which have been diluted in a precursor carrier medium at significantly reduced precursor concentration levels to allow accurate and repeatable copper precursor transport to the reaction zone at a rate and flux which allow reproducible deposition of ultrathin copper layers, e.g., as thin as 10-15A, within 1-2A accuracy.
  • additional, tighter, control on ultrathin layer thickness could be achieved by combining the approach above with using copper source precursors of low volatility.
  • a substrate bias when needed, to form a soft plasma region above the substrate leads to significant enhancement in the rate of impingement on the substrate of copper and aluminum ions from the copper and aluminum precursor gases, leading to more conformal coating of the topographies of microelectronics device structures.
  • Substrate bias leads to a significant enhancement in the flux of copper and aluminum ions impinging on the substrate and a corresponding increase in the re-emission probability of such atoms inside via and trench structures.
  • These re- emission processes are known to create improved step coverage in patterned holes, vias, and trenches with aggressive aspect ratios (0.25 ⁇ m features with 4 to 1 aspect ratios and beyond). This feature is especially useful when the CVD growth mode is reaction rate limited, or when the flux of precursor species to the CVD reaction zone is restricted to significantly reduced concentrations.
  • copper-doped aluminum films can be prepared in-situ, i.e., without the necessity of transferring a substrate coated with a single film (Al or Cu) to another reaction chamber to deposit the other film.
  • This approach allows either in-situ deposition of sequential bilayers of Al and Cu followed by in-situ or ex-situ annealing.
  • Our process can also be applied to coatings for refractive, mechanical, optoelectronic, or decorative applications in applications other than microelectronic.
  • Plasma assisted chemical vapor deposition (PACVD) of copper was carried out with the reactor shown in FIG. 1, using copper n-n' dimethyl diketenimidate as the copper source.
  • the copper source precursor 10 was placed in the bubbler/sublimator 11 which was heated by a combination constant temperature bath and associated power supply 12 to temperatures between 100 and 150°C during the CVD process. All transport and delivery lines and high vacuum isolation valves 18, 19, and 20 were maintained at temperatures in the range 100 to 150°C, using a combination heating tape and associated power supply 21 and 22 to prevent precursor recondensation.
  • the reactor was an 8" wafer, cold wall stainless steel CVD reactor. It was equipped with a parallel plate type plasma configuration made of two electrodes 26 and 27, with the reactor itself providing electrical grounding.
  • the upper plate 26 served as the active electrode and was driven by the radio frequency (13.56 MHz) power supply 28. It was constructed in a "mesh" type pattern to allow unconstricted reactant flow to the substrate.
  • a hydrogen plasma was used for in-situ predeposition substrate cleaning at plasma power densities in the range 0.05-0.25 W/cm 2 , while a hydrogen plasma power density in the range 0.01 to 2.5 W/cm 2 was employed during actual deposition for PACVD copper.
  • the substrate which consisted of either unpatterned or patterned Si and SiO 2 and TiN coated Si and SiO 2 wafers, was placed on the lower electrode 27, which was not biased in this case, and was heated to processing temperatures in the range 100-250°C by an aluminum-encapsulated resistive heater 30.
  • the cone shaped shower head 20 was employed to ensure proper reactant mixing and uniformity in reactant delivery and flow over 8" wafers.
  • the reactor was periodically baked under a hydrogen atmosphere to below 0.2 Torr and then pumped down to below IO "7 Torr for an hour at 150°C.
  • the pumping stack 32 consisted of two pumping packages, the first is turbomolecular pump based, and the second roots blower pump based, and was isolated from the reactor by the high vacuum gate valve.
  • the turbomolecular pump based package was used to ensure high vacuum base pressure in the reactor, while the roots blower based package was employed for appropriate handling of the high gas throughput during actual CVD runs.
  • a high vacuum load lock system was used for transport and loading of 8" wafers into the reactor.
  • a side line 25 was employed to feed the hydrogen gas into the reactor.
  • the H 2 flow Of 100 to 1000 seem was controlled by a mass flow controller 23 and associated isolation valve 24.
  • the copper deposition step was immediately followed in-situ with thermal CVD of aluminum using dimethylethyl aluminum alane (DME4AA) as the source precursor.
  • the aluminum source precursor DMEAA 35 is placed in the reservoir (bubbler/sublimator) 36 in FIG. 1 which could be heated by a combination constant temperature oil bath and associated power supply 37 to a temperature in the range 20-60°C during the CVD process. This temperature range was selected to ensure the vaporization of the aluminum source, while avoiding its premature decomposition.
  • An MKS Model 1150 hot source mass flow controller 41 was used to control the flow of precursor, which ranged from 0.5 to 10 seem, into the CVD system through inlet 40.
  • the aluminum delivery system could be isolated from the precursor reservoir by a high vacuum valve 42.
  • All transport and delivery lines and high vacuum isolation valves 40, 41 and 42, were maintained at the aluminum precursor vaporization temperature (20-60°C), using a typical combination of resistance heating tape and associated power supply 43, to prevent precursor recondensation.
  • the aluminum film was grown in-situ on the top of the copper seed layer at substrate temperature of 120-250°C, hydrogen reactant flow of 100-1000 seem, and reactor working pressure of 100-2000 mtorr. After the aluminum deposition step was completed, ex-situ annealing of the Al/Cu bilayer was performed for 100 minutes at 450°C in a hydrogen ambient at a working pressure of 1 atmosphere.
  • the Cu doped Al films thus produced were metallic, continuous, and silver colored. Their structural and electrical properties as well as chemical composition, were thoroughly analyzed by x-ray diffraction (XRD), Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS), Rutherford backscattering (RBS), four point resistivity probe, and cross-sectional SEM (CS-SEM).
  • XRD x-ray diffraction
  • AES Auger electron spectroscopy
  • XPS x-ray photoelectron spectroscopy
  • RBS Rutherford backscattering
  • CS-SEM cross-sectional SEM
  • An Atomic force microscopy scan of the surface of the 380 ⁇ A-thick copper-doped aluminum film indicates a smooth surface mo ⁇ hology with small aluminum grains. This is in contrast to the surface mo ⁇ hology of a 720 ⁇ A-thick aluminum film grown by thermal CVD without a copper seed layer, as displayed in FIG. 5, where AFM shows a rough surface mo ⁇ hology with extremely large aluminum grains.
  • Four point probe resistivity measurements showed an after annealing resistivity for the Cu doped Al film of 3.49 ⁇ cm.
  • XRD x-ray diffraction
  • AES Auger electron spectroscopy
  • XPS x-ray photoelectron spectroscopy
  • RBS Rutherford backscattering
  • CS-SEM cross-sectional SEM
  • An Atomic force microscopy scan of the surface of the 800 ⁇ A-thick copper- doped aluminum film indicates a smooth surface mo ⁇ hology widi small aluminum grains. This is in contrast to the surface mo ⁇ hology of a 7200A-thickA-aluminum film grown by thermal CVD without a copper seed layer.
  • the AFM grain size data shown in the Table demonstrates the role of the copper seed layer in forming an Al-Cu phase with smooth surface mo ⁇ hology and corresponding small grain size (more than 50 times smaller than an aluminum film of comparable thickness grown by conventional thermal CVD Al without Cu seed layer).
  • the present invention was applied to grow and anneal PACVD deposited
  • Al-Cu-Al trilayer stacks The purpose was to demonstrate the applicability of the present
  • the first 1000A thick aluminum layer was deposited by plasma assisted chemical vapor deposition (PACVD) in the reactor shown in FIG. 1, using DMEAA as the aluminum source.
  • PSVD plasma assisted chemical vapor deposition
  • the aluminum precursor and hydrogen reactant gaseous flows were set at, respectively, 10 seem and 1000 seem.
  • the substrate temperature, plasma power, lOand reactor working pressure were, respectively, 1570, 0.15 torr, and 3 watts, with a bias of 150 kHz and 5W being applied to the substrate to ensure conformal Al deposition in aggressive patterned structures, such as 0.25 pm, 4:1, aspect ratio vias and trenches of semiconductor substrates.
  • the reactor was pumped down below IO "7 torr to
  • 25substrate temperature, plasma power, and reactor working pressure were, respectively, 157°C, 0.5 torr, and 30 watts, with no substrate bias.
  • the reactor was again pumped down below IO '7 torr to ensure complete removal for any copper precursor species. This step was immediately followed in- situ with PACVD of aluminum from DMEAA under the same process parameter used for the
  • the Cu doped Al films thus produced were metallic, continuous, and silver colored. Their structural and electrical properties as well as chemical composition, were thoroughly analyzed by x-ray diffraction (XRD), Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS), Rutherford backscattering (RBS), four point resistivity probe, and cross- sectional SEM (CS-SEM). After annealing, the film consisted of an Al-0.1 at% Cu phase, with the copper being uniformly distributed across the aluminum matrix, as documented by the RBS data shown in FIG. 8.
  • XRD x-ray diffraction
  • AES Auger electron spectroscopy
  • XPS x-ray photoelectron spectroscopy
  • RBS Rutherford backscattering
  • CS-SEM cross- sectional SEM
  • Preparation ofCu doped Al films usine different Al precursor flows
  • sequential, plasma assisted chemical vapor deposition (PACVD) of copper followed by thermal CVD of aluminum was carried out with the reactor shown in FIG. 1 , using the same source precursors and run conditions used for Example 1 , except for aluminum precursor gaseous flow.
  • Two different aluminum precursor flows namely 5 seem and 15 seem, were employed to demonstrate that the application of an ultrathin ( ⁇ 10 ⁇ A) copper layer as a seed layer in the deposition of smooth, copper-doped, aluminum films with the texture and mo ⁇ hology needed for advanced microelectronics applications is independent of aluminum precursor flow and associated nucleation mechanisms and film thickness.
  • specialized semiconductor cantilever structures which consisted of silicon substrates upon which "overhang" silicon oxide patterns, were formed, were also employed to examine film step coverage and conformality.
  • the Cu doped Al films thus produced were metallic, continuous, and silver colored. Their structural and electrical properties as well as chemical composition, were thoroughly analyzed by x-ray diffraction (XRD), Auger electron spectroscopy (AES), x-ray photoelectron spectroscopy (XPS), Rutherford backscattering (RBS), four point resistivity probe, and cross- sectional SEM (CS-SEM).
  • XRD x-ray diffraction
  • AES Auger electron spectroscopy
  • XPS x-ray photoelectron spectroscopy
  • RBS Rutherford backscattering
  • CS-SEM cross- sectional SEM
  • FIG. 9 depicts cross sections, magnified by scanning electron microscopy, of the semiconductor cantilever structures after copper and aluminum deposition.
  • aluminum was deposited directly on the overhang structure by conventional thermal CVD without using the copper seed layer.
  • the present invention was applied to grow an Al-Cu stack consisting of approximately 750 ⁇ A-thick Al film on an ultrathin copper seed layer.
  • Aluminum precursor flow was 5 seem in both cases.
  • a comparison of the two cross 5 sections demonstrates how the ultrathin copper seed layer inhibits undesirable large aluminum grain growth, yielding the texture and composition required for microelectronics applications.
  • FIG. 10 also depicts cross sections, magnified by scanning electron microscopy, of the semiconductor cantilever structures after copper and aluminum deposition. In FIG.
  • Example 5 Preparation of ultrathin Cu layers with reproducible thickness
  • the present invention was applied to demonstrate the reproducible growth of ultrathin copper layers ( ⁇ 10 ⁇ A) through the use of mixtures of copper source precursors
  • plasma assisted chemical vapor deposition (PACVD) of copper was carried out with the reactor shown in FIG. 1, using the precursor copper bis-hexafluoroacetylacetonate, Cu(hfac) 2 as the copper source.
  • the copper source precursor copper bis-hexafluoroacetylacetonate, Cu(hfac) 2 as the copper source.
  • An MKS (Andover, Massachusetts) liquid delivery system 41 consisting of a combination micropump and vaporizer head was applied to the delivery of the liquid (precursor + medium) at a rate of 0.4 cc/min to the CVD reactor 17. All transport and delivery lines and high vacuum isolation valves 18, 19, and 20 were maintained at temperatures in the range 50 to 100°C, using a combination heating tape and associated power supply 21 and 22, to prevent precursor recondensation.
  • the reactor was an 8" wafer, cold wall stainless steel CVD reactor. It was equipped with a parallel plate type plasma configuration made of two electrodes 26 and 27, with the reactor itself providing electrical grounding.
  • the upper plate 26 served as the active electrode and was driven by the radio frequency (13.56 MHz) power supply 28. It was constructed in a "mesh" type pattern to allow unconstricted reactant flow to the substrate.
  • a hydrogen lOplasma was used for in-situ predeposition substrate cleaning at plasma power densities in the range 0.05-0.25 W/cm 2 , while a hydrogen plasma power density in the range 0.01 to 2.5 W/cm 2 was employed during actual deposition for PACVD copper.
  • the substrate which consisted of either unpatterned or patterned Si and SiO 2 and TiN coated Si and SiO 2 wafers, was placed on the lower electrode 27, which was not biased in this case, and was heated to
  • the reactor was periodically baked under a hydrogen atmosphere to below 0.2 Torr and then pumped down to below IO "7 Torr for an hour at
  • the pumping stack 32 consisted of two pumping packages, the first is turbomolecular pump based, and the second roots blower pump based, and was isolated from the reactor by the high vacuum gate valve.
  • the turbomolecular pump based package was used to ensure high vacuum base pressure in the reactor, while the roots blower based package was employed for appropriate handling of the high gas throughput during actual CVD runs.
  • the Cu ultrathin layers thus produced were metallic, continuous, and copper colored.
  • RBS analysis showed a highly repeatable thickness of 8 ⁇ A in all 10 reproducibility runs, regardless of the substrate used. This result is documented in FIG. 11 and FIG. 12 which compare the thickness of the Cu ultrathin layer for two sets of runs performed on Si (FIG. 1 1) and TiN (FIG. 12). All four samples exhibit 5 a thickness of 80 A.
  • the apparatus and method disclosed above are also useful in providing a seed layer for copper electroplating.
  • the fine grain mo ⁇ hology of the layers made with the apparatus and method overcomes the disadvantages of sputter deposited films.
  • the deposited layers are more conformal to the surface of the wafer than are sputtered layers.
  • the deposited layers lOare also smoother than sputtered layers. Such characteristics allow one skilled in the art to build a larger capacitor on a semiconductor substrate with aluminum plates than is possible with sputter deposited aluminum films.

Abstract

Cette invention concerne un procédé et un appareil permettant de former sur un substrat structuré (29) un aluminium conforme pur et des revêtements dopés en aluminium. Le procédé consiste à utiliser des techniques de déposition de vapeur thermique et photochimique à basse température, et à polariser un substrat (29) au moyen d'une électrode inférieure (27) et d'un générateur de fréquence (31) pour former des couches simples et des couches doubles conformes constituées d'un A1 pur et/ou d'un A1 dopé sur des substrats à semi-conducteurs comportant des trous à dessins, des vias et des tranchées ayant des rapports d'aspect agressif. L'utilisation de la déposition de vapeur photochimique (Photo-CVD), pour laquelle des densités de plasma de faible puissance sont employées, favorise la formation de films d'aluminium présentant une morphologie de la surface lisse et une petite taille de grain, nécessaires pour des applications USLI, tandis que la polarisation du substrat assure aux dispositifs une couverture supérieure et un revêtement en aluminium complet, intrinsèques à la fabrication d'articles de micro-électronique. Le dopage de l'aluminium est réalisé par dépôt, par photo-CVD, de couches doubles d'A1 et de Cu suivi d'un recuit local, ou par déposition locale simultanée de vapeur photochimique d'aluminium dopé de cuivre.
PCT/US1997/010435 1996-06-14 1997-06-13 Methodologie et appareil de dopage local de revetements en aluminium WO1997047783A1 (fr)

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SG86443A1 (en) * 1999-09-27 2002-02-19 Applied Materials Inc Method and apparatus of forming a sputtered doped seed layer
WO2002043116A2 (fr) * 2000-11-01 2002-05-30 Applied Materials, Inc. Attaque de caracteristiques a rapport de forme eleve dans un substrat
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WO2013043507A1 (fr) * 2011-09-23 2013-03-28 Applied Materials, Inc. Films en alliage de métal-aluminium composés de précurseurs de pcai métallique et de précurseurs d'aluminium
CN112981368A (zh) * 2021-02-03 2021-06-18 北航（四川）西部国际创新港科技有限公司 一种改进的cvd设备、以及用改进的cvd设备实现共渗沉积铝硅涂层的制备方法

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Publication number Priority date Publication date Assignee Title
US6534133B1 (en) 1996-06-14 2003-03-18 Research Foundation Of State University Of New York Methodology for in-situ doping of aluminum coatings
SG86443A1 (en) * 1999-09-27 2002-02-19 Applied Materials Inc Method and apparatus of forming a sputtered doped seed layer
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WO2002043116A2 (fr) * 2000-11-01 2002-05-30 Applied Materials, Inc. Attaque de caracteristiques a rapport de forme eleve dans un substrat
WO2002043116A3 (fr) * 2000-11-01 2003-05-01 Applied Materials Inc Attaque de caracteristiques a rapport de forme eleve dans un substrat
WO2013043507A1 (fr) * 2011-09-23 2013-03-28 Applied Materials, Inc. Films en alliage de métal-aluminium composés de précurseurs de pcai métallique et de précurseurs d'aluminium
CN112981368A (zh) * 2021-02-03 2021-06-18 北航（四川）西部国际创新港科技有限公司 一种改进的cvd设备、以及用改进的cvd设备实现共渗沉积铝硅涂层的制备方法
CN112981368B (zh) * 2021-02-03 2022-06-07 北航（四川）西部国际创新港科技有限公司 一种改进的cvd设备、以及用改进的cvd设备实现共渗沉积铝硅涂层的制备方法

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