WO2003102266A1 - Deposition of copper films - Google Patents

Deposition of copper films Download PDF

Info

Publication number
WO2003102266A1
WO2003102266A1 PCT/US2003/017367 US0317367W WO03102266A1 WO 2003102266 A1 WO2003102266 A1 WO 2003102266A1 US 0317367 W US0317367 W US 0317367W WO 03102266 A1 WO03102266 A1 WO 03102266A1
Authority
WO
WIPO (PCT)
Prior art keywords
period
copper
exposure
containing precursor
reducing gas
Prior art date
Application number
PCT/US2003/017367
Other languages
French (fr)
Inventor
Ling Chen
John A. Norman
Mei Chang
Original Assignee
Applied Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Applied Materials, Inc. filed Critical Applied Materials, Inc.
Priority to CN03817559.2A priority Critical patent/CN1671883B/en
Priority to JP2004510498A priority patent/JP2005528808A/en
Publication of WO2003102266A1 publication Critical patent/WO2003102266A1/en

Links

Classifications

    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H01L21/28562—Selective deposition

Definitions

  • Embodiments of the present invention generally relate to a method of copper film deposition and, more particularly to a method of copper film deposition using cyclical deposition techniques.
  • VLSI very large scale integration
  • ULSI ultra large scale integration
  • the multilevel interconnects that lie at the heart of this technology require the filling of contacts, vias, lines, and other features formed in high aspect ratio apertures. Reliable formation of these features is very important to the success of both VLSI and ULSI as well as to the continued effort to increase circuit density and quality on individual substrates and die.
  • the widths of contacts, vias, lines and other features, as well as the dielectric materials between them may decrease to less than about 250 nm (nanometers), whereas the thickness of the dielectric layers remains substantially constant, with the result that the aspect ratios for the features, i.e., their height divided by width, increases.
  • Many conventional deposition processes have difficulty filling structures where the aspect ratio exceeds 4:1 , and particularly where the aspect ratio exceeds 10:1. As such, there is a great amount of ongoing effort being directed at the formation of void-free, nanometer-sized structures having aspect ratios wherein the ratio of feature height to feature width can be 8:1 or higher.
  • Elemental aluminum (Al) and its alloys have been the traditional metals used to form vias and lines in semiconductor devices because of aluminum's perceived low electrical resistivity, its superior adhesion to most dielectric materials, its ease of patterning, and the ability to obtain it in a highly pure form.
  • Al has a higher electrical resistivity than other more conductive metals such as copper (Cu), and aluminum also can suffer from electromigration leading to the formation of voids in the conductor.
  • Copper (Cu) and its alloys have lower resistivities than aluminum as well as a significantly higher electromigration resistance compared to aluminum. These characteristics are important for supporting the higher current densities experienced at high levels of integration and increased device speed. Copper also has good thermal conductivity. Therefore, copper is becoming a choice metal for filling sub- quarter micron, high aspect ratio interconnect features on semiconductor substrates.
  • FIGS. 1A-1B illustrate the possible consequences of material layer deposition in a high aspect ratio feature 6 on a substrate 1.
  • the high aspect ratio feature 6 may be any opening such as a space formed between adjacent dielectric material layers 2, such as a contact, via or trench.
  • a copper layer 11 that is formed using conventional deposition techniques (e.g., chemical vapor deposition (CVD), physical vapor deposition (PVD) and electroplating) tends to be deposited on the top edges 6T of the feature 6 at a higher rate than at the bottom 6B or sides 6S thereof, creating an overhang.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • electroplating e.g., electroplating
  • This overhang or excess deposition of material is sometimes referred to as crowning. Such excess material continues to build up on the top edges 6T of the feature 6, until the opening is closed off by the deposited copper layer 11 , forming a void 14 therein. Additionally, as shown in FIG. 1 B, a seam 8 may be formed when the copper layer 11 deposited on both sides 6S of the feature 6 opening merges. The presence of either voids or seams may result in unreliable integrated circuit performance.
  • a method of forming a copper film on a substrate is described.
  • the copper film is formed using a cyclical deposition technique by alternately adsorbing a copper-containing precursor and a reducing gas on a substrate.
  • the copper film formation is compatible with integrated circuit fabrication processes.
  • the copper film may be used as interconnect metallization.
  • a preferred process sequence includes providing a substrate having an interconnect pattern defined in one or more dielectric layers formed thereon.
  • the interconnect pattern includes a barrier layer conformably deposited thereon.
  • the interconnect pattern is filled with copper (Cu) metallization using a cyclical deposition technique by alternately adsorbing a copper-containing precursor and a reducing gas on the substrate.
  • FIGS. 1A-1 B are cross-sectional views of possible deposition results for high aspect ratio features filled using conventional prior art deposition processes
  • FIG. 2 depicts a schematic cross-sectional view of a process chamber that can be used for the practice of embodiments described herein;
  • FIG. 3 illustrates a process sequence for the formation of a copper film using cyclical deposition techniques according to one embodiment described herein;
  • FIG. 4 illustrates a process sequence for the formation of a copper film using cyclical deposition techniques according to an alternate embodiment described herein;
  • FIGS. 5A-5B illustrate schematic cross-sectional views of an integrated circuit at different stages of an interconnect fabrication sequence.
  • FIG. 2 depicts a schematic cross-sectional view of a process chamber
  • the process chamber 200 includes a substrate support 212, which is used to support a substrate 210 within the process chamber 200.
  • the substrate support 212 is moveable in a vertical direction inside the process chamber 200 using a displacement mechanism 214.
  • the substrate support may also include a vacuum chuck (not shown), an electrostatic chuck (not shown), or a clamp ring (not shown) for securing the substrate 210 thereto during a deposition sequence.
  • the substrate 210 may be heated to some desired temperature prior to or during deposition.
  • the substrate support 212 may be heated using an embedded heater element (not shown).
  • the substrate support 212 may be resistively heated by applying an electric current from an AC power supply (not shown) to the heater element (not shown).
  • the substrate 210 is, in turn, heated by the substrate support 212.
  • the substrate support may be heated using radiant heaters such as, for example, lamps (not shown).
  • a gas delivery system 230 is disposed on an upper portion of the process chamber 200.
  • the gas delivery system 230 provides process gases to the process chamber 200.
  • the gas delivery system 230 may comprise a chamber lid 232.
  • the chamber lid 232 includes an expanding channel 234 extending from a central portion of the chamber lid 232 as well as a bottom surface 260 extending from the expanding channel 234 to a peripheral portion of the chamber lid 232.
  • the bottom surface 260 of the chamber lid 232 is sized and shaped to substantially cover the substrate 210 disposed on the substrate support 212.
  • the expanding channel 234 also includes gas inlets 236A, 236B through which gases are provided thereto.
  • the gas inlets 236A, 236B are coupled to electronic control valves 242A, 242B, 252A, 252B.
  • Electronic control valves 242A, 242B may be coupled to process gas sources 238, 239, respectively, while electronic control valves 252A, 252B may be coupled to a gas source 240.
  • the electronic control valves 242A, 242B, 252A, 252B as used herein refer to any control valve capable of providing rapid and precise gas flow to the process chamber 200 with valve open and close cycles of less than about 1-2 seconds, and more preferably less than about 0.1 second. Proper control and regulation of gas flows to the gas delivery system 230 are performed by a microprocessor controller 280.
  • the microprocessor controller 280 may be one of any form of general purpose computer processor (CPU) that can be used in an industrial setting for controlling various chambers and sub-processors.
  • the computer may use any suitable memory, such as random access memory, read only memory, floppy disk drive, hard disk, or any other form of digital storage, local or remote.
  • Various support circuits may be coupled to the CPU for supporting the processor in a conventional manner.
  • Software routines as required may be stored in the memory or executed by a second CPU that may be remotely located.
  • the software routines when executed, transform the general purpose computer into a specific process computer that controls the chamber operation so that a chamber process is performed.
  • software routines may be used to precisely control the activation of the electronic control valves for the execution of process sequences according to embodiments described herein.
  • the software routines may be performed in hardware, as an application specific integrated circuit or other type of hardware implementation, or a combination of software or hardware.
  • a method of forming a copper layer on a substrate is described.
  • the copper layer is formed using a cyclic deposition technique.
  • FIG. 3 illustrates an embodiment of a cyclical deposition process sequence 300 according to the present invention detailing the various steps used for the formation of the copper layer utilizing a constant carrier gas flow. These steps may be performed in a process chamber similar to that described above with respect to FIG. 2.
  • a substrate is provided to a process chamber.
  • the substrate may be for example, a silicon substrate having an interconnect pattern defined in one or more dielectric material layers formed thereon.
  • the process chamber conditions such as, for example, the temperature and pressure are adjusted to enhance the adsorption of the process gases on the substrate.
  • the process chamber should be maintained at a temperature less than about 180 S C and a pressure within a range of about 1 torr to about 10 torr.
  • a carrier gas stream is established within the process chamber, as indicated in step 304.
  • Carrier gases may be selected so as to also act as a purge gas for the removal of volatile reactants and/or by-products from the process chamber.
  • Carrier gases such as, for example, helium (He) and argon (Ar), and combinations thereof, among others may be used.
  • a pulse of a copper-containing precursor is added to the carrier gas stream.
  • the term pulse as used herein refers to a dose of material added to the carrier gas stream.
  • the pulse of the copper-containing precursor lasts for a predetermined interval.
  • the time interval for the pulse of the copper-containing precursor is variable depending on 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 reactants used.
  • a large-volume process chamber may lead to a longer time to stabilize the process conditions such as, for example, carrier purge gas flow and temperature, requiring a longer pulse time; (2) a lower flow rate for the process gas may also lead to a longer time to stabilize the process conditions, requiring a longer pulse time; and (3) a lower chamber pressure means that the process gas is evacuated from the process chamber more quickly, requiring a longer pulse time.
  • the process conditions are advantageously selected so that a pulse of the copper-containing precursor provides a sufficient amount of precursor so that at least a monolayer of the copper-containing precursor is adsorbed on the substrate. Thereafter, excess copper-containing precursor remaining in the chamber may be removed from the process chamber by the constant carrier gas stream in combination with the vacuum system.
  • step 308 after the excess copper-containing precursor has been removed from the process chamber by the constant carrier gas stream, a pulse of a reducing gas is added to the carrier gas stream.
  • the pulse of the reducing gas also lasts for a predetermined time interval that is variable as described above with reference to the copper-containing precursor.
  • the time interval for the pulse of the reducing gas should be long enough for adsorption of at least a monolayer of the reducing gas on the copper-containing precursor.
  • excess reducing gas remaining in the chamber may be removed therefrom by the constant carrier gas stream in combination with the vacuum system.
  • Steps 304 through 308 comprise one embodiment of a deposition cycle for copper layer deposition.
  • a constant flow of the carrier gas is provided to the process chamber modulated by alternating periods of pulsing and non-pulsing where the periods of pulsing alternate between the copper- containing precursor and the reducing gas along with the carrier gas stream, while the periods of non-pulsing include only the carrier gas stream.
  • the time interval for each of the pulses of the copper-containing precursor and the reducing gas may have the same duration. That is, the duration of the pulse of the copper-containing precursor may be identical to the duration of the pulse of the reducing gas.
  • a time interval (T for the pulse of the copper-containing precursor equals a time interval (T 2 ) for the pulse of the reducing gas.
  • the time interval for each of the pulses of the copper- containing precursor and the reducing gas may have different durations. That is, the duration of the pulse of the copper-containing precursor may be shorter or longer than the duration of the pulse of the reducing gas.
  • the time interval (T t ) for the pulse of the copper-containing precursor is different than the time interval (T 2 ) for the pulse of the reducing gas.
  • the periods of non-pulsing between each of the pulses of the copper-containing precursor and the reducing gas may have the same duration. That is, the duration of the period of non-pulsing between each pulse of the copper- containing precursor and each pulse of the reducing gas may be identical.
  • a time interval (T 3 ) of non-pulsing between the pulse of the copper- containing precursor and the pulse of the reducing gas equals a time interval (T 4 ) of non-pulsing between the pulse of the reducing gas and the pulse of the copper- containing precursor.
  • the periods of non-pulsing between each of the pulses of the copper-containing precursor and the reducing gas may have different durations. That is, the duration of the period of non-pulsing between each pulse of the copper- containing precursor and each pulse of the reducing gas may be shorter or longer than the duration of the period of non-pulsing between each pulse of the reducing gas and the pulse of the copper-containing precursor.
  • a time interval (T 3 ) of non-pulsing between the pulse of the copper-containing precursor and the pulse of the reducing gas is different from a time interval (T 4 ) of non-pulsing between the pulse of the reducing gas and the pulse of the copper-containing precursor.
  • the time intervals for each pulse of the copper-containing precursor, the reducing gas and the periods of non-pulsing therebetween for each deposition cycle may have the same duration.
  • a time interval (T for the pulse of the copper-containing precursor, a time interval (T 2 ) for the pulse of the reducing gas, a time interval (T 3 ) of non-pulsing between the pulse of the copper-containing precursor and the pulse of the reducing gas and a time interval (T 4 ) of non-pulsing between the pulse of the reducing gas and the pulse of the copper-containing precursor each have the same value for each deposition cycle.
  • a time interval (TO for the pulse of the copper-containing precursor has the same duration as the time interval (Ti) for the pulse of the copper-containing precursor in subsequent deposition cycles (C 2 ...CN).
  • the duration of each pulse of the reducing gas as well as the periods of non-pulsing between the pulse of the copper-containing precursor and the reducing gas in the first deposition cycle (d) is the same as the duration of each pulse of the reducing gas and the periods of non-pulsing between the pulse of the copper- containing precursor and the reducing gas in subsequent deposition cycles (C 2 ...C N ), respectively.
  • the time intervals for at least one pulse of the copper- containing precursor, the reducing gas and the periods of non-pulsing therebetween for one or more of the deposition cycles of the copper layer may have different durations.
  • one or more of the time intervals (T for the copper-containing precursor, the time intervals (T 2 ) for the reducing gas, the time intervals (T 3 ) of non-pulsing between the pulse of the copper-containing precursor and the pulse of the reducing gas and the time intervals (T 4 ) of non-pulsing between the pulse of the reducing gas and the pulse of the copper-containing precursor may have different values for one or more deposition cycles of the cyclical deposition process.
  • the time interval (TO for the pulse of the copper-containing precursor may be longer or shorter than the time interval (TO for the pulse of the copper-containing precursor in subsequent deposition cycles (C 2 ...C N ).
  • the duration of each pulse of the reducing gas and the periods of non-pulsing between the pulse of the copper-containing precursor and the reducing gas in the first deposition cycle (CO may be the same or different than the duration of corresponding pulses of the reducing gas and periods of non-pulsing between the pulse of the copper-containing precursor and the reducing gas in subsequent deposition cycles (C 2 ...C N ), respectively.
  • step 310 after each deposition cycle (steps 304 through 308) a thickness of the copper will be formed on the substrate. Depending on specific device requirements, subsequent deposition cycles may be needed to achieve a desired thickness. As such, steps 304 through 308 are repeated until the desired thickness for the copper layer is achieved. Thereafter, when the desired thickness for the copper layer is achieved the process is stopped as indicated by step 212.
  • a copper layer deposition sequence 400 includes providing a substrate to the process chamber and adjusting the process chamber conditions (step 402), providing a first pulse of a purge gas to the process chamber (step 404), providing a pulse of a copper-containing precursor to the process chamber (step 406), providing a second pulse of a purge gas to the process chamber (step 408), providing a pulse of a reducing gas to the process chamber (step 410), and then repeating steps 404 through 410, or stopping the deposition process (step 414) depending on whether a desired thickness for the copper layer has been achieved (step 412).
  • the time intervals for each of the pulses of the copper-containing precursor, the reducing gas and the purge gas may have the same or different durations as discussed above with respect to FIG. 3.
  • corresponding time intervals for one or more pulses of the copper-containing precursor, the reducing gas and the purge gas in one or more of the deposition cycles of the copper layer deposition process may have different durations.
  • the copper layer deposition cycle is depicted as beginning with a pulse of the copper-containing precursor followed by a pulse of the reducing gas.
  • the copper layer deposition cycle may start with a pulse of the reducing gas followed by a pulse of the copper-containing precursor.
  • the copper-containing precursor may comprise an organometallic copper complex such as, for example, copper +1 ( ⁇ -diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu +1 (hfac)(TMVS)), copper "1"2 hexafluoroacetylacetonate (Cu +2 (hfac) 2 ), copper +2 diacetylacetonate (Cu +2 (acac) 2 ) and 2Cu Me 2 NsiMe2CH2CH 2 SiNMe2, among others.
  • organometallic copper complex such as, for example, copper +1 ( ⁇ -diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu +1 (hfac)(TMVS)), copper "1"2 hexafluoroacetylacet
  • Suitable reducing gases may include for example, silane (SiH 4 ), disilane (S- 2 H 6 ), dimethylsilane (SiC 2 H 8 ), methyl silane (SiCH 6 ), ethylsilane (SiC 2 H 8 ), borane (BH 3 ), diborane (B 2 H 6 ), triborane (B 3 H 9 ), tetraborane (B 4 H 12 ), pentaborane (B 5 H1 5 ), hexaborane (B 6 H ⁇ 8 ), heptaborane (B 7 H 2 ⁇ ), octaborane (B 8 H2 4 ), nanoborane (B9H27) and decaborane (B1 0 H 30 ), among others.
  • silane SiH 4
  • disilane S- 2 H 6
  • dimethylsilane SiC 2 H 8
  • methyl silane SiCH 6
  • ethylsilane SiC 2 H 8
  • One exemplary process of depositing a copper layer comprises sequentially providing pulses of copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu +1 (hfac)(TMVS)) and pulses of diborane (B 2 H 6 ).
  • the copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu +1 (hfac)(TMVS) may be provided to an appropriate flow control valve, for example, an electronic control valve, at a flow rate of between about 0.01 seem (standard cubic centimeters per minute) and about 5 seem, preferably between about 0.1 seem and about 1 seem, and thereafter pulsed for about 5 seconds or less, preferably about 1 second or less.
  • the diborane (B H 6 ) may be provided to an appropriate flow control valve, for example, an electronic flow control valve, at a flow rate of between about 1 seem to about 80 seem, preferably between about 10 seem and about 50 seem, and thereafter pulsed for about 10 seconds or less, preferably about 2 seconds or less.
  • the substrate may be maintained at a temperature less than about 180 °C, preferably about 120 °C at a chamber pressure between about 0.1 torr to about 10 torr, preferably about 1 torr.
  • Another exemplary process of depositing a copper layer comprises sequentially providing pulses of copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu +1 (hfac)(TMVS)) and pulses of silane (SiH 4 ).
  • the copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu +1 (hfac)(TMVS) may be provided to an appropriate flow control valve, for example, an electronic control valve, at a flow rate of between about 0.1 seem (standard cubic centimeters per minute) and about 5 seem, preferably between about 0.1 seem and about 1 seem, and thereafter pulsed for about 5 seconds or less, preferably about 1 second or less.
  • the silane (SiH 4 ) may be provided to an appropriate flow control valve, for example, an electronic flow control valve, at a flow rate of between about 1 seem to about 100 seem, preferably between about 10 seem and about 50 seem, and thereafter pulsed for about 10 seconds or less, preferably about 2 seconds or less.
  • the substrate may be maintained at a temperature less than about 180 °C, preferably about 120 °C at a chamber pressure between about 0.1 torr to about 10 torr, preferably about 1 torr.
  • FIGS. 5A-5B illustrate cross-sectional views of a substrate at different stages of a copper interconnect fabrication sequence incorporating the copper layer of the present invention.
  • FIG. 5A illustrates a cross-sectional view of a substrate 500 having metal contacts 504 and a dielectric layer 502 formed thereon.
  • the substrate 500 may comprise a semiconductor material such as, for example, silicon (Si), germanium (Ge), or gallium arsenide (GaAs).
  • the dielectric layer 502 may comprise an insulating material such as, for example, silicon oxide or silicon nitride, among others.
  • the metal contacts 504 may comprise for example, copper (Cu), among others.
  • Apertures 504H may be defined in the dielectric layer 502 to provide openings over the metal contacts 504.
  • the apertures 504H may be defined in the dielectric layer 502 using conventional lithography and etching techniques.
  • a barrier layer 506 may be formed in the apertures 504H defined in the dielectric layer 502.
  • the barrier layer 506 may include one of more refractory metal- containing layers such as, for example, titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN), tantalum suicide nitride and titanium suicide nitride, among others.
  • the barrier layer 506 may be formed using a suitable deposition process.
  • titanium nitride may be deposited with a chemical vapor deposition (CVD) process from a reaction of titanium tetraehloride (TiCI 4 ) and ammonia (NH 3 ).
  • TiCI 4 titanium tetraehloride
  • NH 3 ammonia
  • Titanium suicide nitride (TiSiN) may be deposited by forming a titanium nitride (TiN) layer via thermal decomposition of tetrakis(dimethylamido) titanium (TDMAT) followed by exposure to silane (SiH 4 ).
  • the apertures 504H may be filled with copper (Cu) metallization to complete the copper interconnect.
  • Cu copper
  • the copper metallization is formed using the cyclical deposition techniques described above with respect to FIGS. 3-4.

Abstract

A method of forming a copper film on a substrate is described. The copper film is formed using a cyclical deposition technique by alternately adsorbing a copper-containing precursor and a reducing gas on a substrate. One or more of the time intervals for the copper-containing precursor, the time intervals for the reducing gas and the time intervals of non-pulsing may have different values for one or more deposition cycles of the cyclical deposition process. The copper film formation is compatible with integrated circuit fabrication processes. In one integrated circuit fabrication process, the copper film may be used as interconnect metallization.

Description

DEPOSITION OF COPPER FILMS
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] Embodiments of the present invention generally relate to a method of copper film deposition and, more particularly to a method of copper film deposition using cyclical deposition techniques.
2. Description of the Related Art
[0002] Sub-quarter micron, multi-level metallization is one of the key technologies for the next generation of very large scale integration (VLSI) and ultra large scale integration (ULSI) semiconductor devices. The multilevel interconnects that lie at the heart of this technology require the filling of contacts, vias, lines, and other features formed in high aspect ratio apertures. Reliable formation of these features is very important to the success of both VLSI and ULSI as well as to the continued effort to increase circuit density and quality on individual substrates and die.
[0003] As circuit densities increase, the widths of contacts, vias, lines and other features, as well as the dielectric materials between them may decrease to less than about 250 nm (nanometers), whereas the thickness of the dielectric layers remains substantially constant, with the result that the aspect ratios for the features, i.e., their height divided by width, increases. Many conventional deposition processes have difficulty filling structures where the aspect ratio exceeds 4:1 , and particularly where the aspect ratio exceeds 10:1. As such, there is a great amount of ongoing effort being directed at the formation of void-free, nanometer-sized structures having aspect ratios wherein the ratio of feature height to feature width can be 8:1 or higher.
[0004] Additionally, as the feature widths decrease, the device current typically remains constant or increases, which results in an increased current density for such feature. Elemental aluminum (Al) and its alloys have been the traditional metals used to form vias and lines in semiconductor devices because of aluminum's perceived low electrical resistivity, its superior adhesion to most dielectric materials, its ease of patterning, and the ability to obtain it in a highly pure form. However, aluminum has a higher electrical resistivity than other more conductive metals such as copper (Cu), and aluminum also can suffer from electromigration leading to the formation of voids in the conductor.
[0005] Copper (Cu) and its alloys have lower resistivities than aluminum as well as a significantly higher electromigration resistance compared to aluminum. These characteristics are important for supporting the higher current densities experienced at high levels of integration and increased device speed. Copper also has good thermal conductivity. Therefore, copper is becoming a choice metal for filling sub- quarter micron, high aspect ratio interconnect features on semiconductor substrates.
[0006] Despite the desirability of using copper for semiconductor device fabrication, choices of fabrication methods for depositing copper into high aspect ratio features greater than 8:1 are limited. FIGS. 1A-1B illustrate the possible consequences of material layer deposition in a high aspect ratio feature 6 on a substrate 1. The high aspect ratio feature 6 may be any opening such as a space formed between adjacent dielectric material layers 2, such as a contact, via or trench. As shown in FIG. 1A, a copper layer 11 that is formed using conventional deposition techniques (e.g., chemical vapor deposition (CVD), physical vapor deposition (PVD) and electroplating) tends to be deposited on the top edges 6T of the feature 6 at a higher rate than at the bottom 6B or sides 6S thereof, creating an overhang. This overhang or excess deposition of material is sometimes referred to as crowning. Such excess material continues to build up on the top edges 6T of the feature 6, until the opening is closed off by the deposited copper layer 11 , forming a void 14 therein. Additionally, as shown in FIG. 1 B, a seam 8 may be formed when the copper layer 11 deposited on both sides 6S of the feature 6 opening merges. The presence of either voids or seams may result in unreliable integrated circuit performance.
[0007] Thus, there is a need for a method of copper deposition into high aspect ratio structures that provide void-free and seam-free fill thereof. SUMMARY OF THE INVENTION
[0008] A method of forming a copper film on a substrate is described. The copper film is formed using a cyclical deposition technique by alternately adsorbing a copper-containing precursor and a reducing gas on a substrate.
[0009] The copper film formation is compatible with integrated circuit fabrication processes. In one integrated circuit fabrication process, the copper film may be used as interconnect metallization. For an interconnect metallization process, a preferred process sequence includes providing a substrate having an interconnect pattern defined in one or more dielectric layers formed thereon. The interconnect pattern includes a barrier layer conformably deposited thereon. The interconnect pattern is filled with copper (Cu) metallization using a cyclical deposition technique by alternately adsorbing a copper-containing precursor and a reducing gas on the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] So that the manner in which the above recited features of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
[0011] It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0012] FIGS. 1A-1 B are cross-sectional views of possible deposition results for high aspect ratio features filled using conventional prior art deposition processes;
[0013] FIG. 2 depicts a schematic cross-sectional view of a process chamber that can be used for the practice of embodiments described herein;
[0014] FIG. 3 illustrates a process sequence for the formation of a copper film using cyclical deposition techniques according to one embodiment described herein; [0015] FIG. 4 illustrates a process sequence for the formation of a copper film using cyclical deposition techniques according to an alternate embodiment described herein; and
[0016] FIGS. 5A-5B illustrate schematic cross-sectional views of an integrated circuit at different stages of an interconnect fabrication sequence.
DETAILED DESCRIPTION
[0017] FIG. 2 depicts a schematic cross-sectional view of a process chamber
200 that can be used for the practice of embodiments described herein. The process chamber 200 includes a substrate support 212, which is used to support a substrate 210 within the process chamber 200. The substrate support 212 is moveable in a vertical direction inside the process chamber 200 using a displacement mechanism 214. The substrate support may also include a vacuum chuck (not shown), an electrostatic chuck (not shown), or a clamp ring (not shown) for securing the substrate 210 thereto during a deposition sequence.
[0018] Depending on the specific deposition process, the substrate 210 may be heated to some desired temperature prior to or during deposition. For example, the substrate support 212 may be heated using an embedded heater element (not shown). The substrate support 212 may be resistively heated by applying an electric current from an AC power supply (not shown) to the heater element (not shown). The substrate 210 is, in turn, heated by the substrate support 212. Alternatively, the substrate support may be heated using radiant heaters such as, for example, lamps (not shown).
[0019] A vacuum pump 278, in communication with a pumping channel 279, is used to evacuate the process chamber 200 and to maintain the pressure inside the process chamber 200. A gas delivery system 230 is disposed on an upper portion of the process chamber 200. The gas delivery system 230 provides process gases to the process chamber 200. [0020] The gas delivery system 230 may comprise a chamber lid 232. The chamber lid 232 includes an expanding channel 234 extending from a central portion of the chamber lid 232 as well as a bottom surface 260 extending from the expanding channel 234 to a peripheral portion of the chamber lid 232. The bottom surface 260 of the chamber lid 232 is sized and shaped to substantially cover the substrate 210 disposed on the substrate support 212. The expanding channel 234 also includes gas inlets 236A, 236B through which gases are provided thereto.
[0021] The gas inlets 236A, 236B are coupled to electronic control valves 242A, 242B, 252A, 252B. Electronic control valves 242A, 242B may be coupled to process gas sources 238, 239, respectively, while electronic control valves 252A, 252B may be coupled to a gas source 240. The electronic control valves 242A, 242B, 252A, 252B as used herein refer to any control valve capable of providing rapid and precise gas flow to the process chamber 200 with valve open and close cycles of less than about 1-2 seconds, and more preferably less than about 0.1 second. Proper control and regulation of gas flows to the gas delivery system 230 are performed by a microprocessor controller 280.
[0022] The microprocessor controller 280 may be one of any form of general purpose computer processor (CPU) that can be used in an industrial setting for controlling various chambers and sub-processors. The computer may use any suitable memory, such as random access memory, read only memory, floppy disk drive, hard disk, or any other form of digital storage, local or remote. Various support circuits may be coupled to the CPU for supporting the processor in a conventional manner. Software routines as required may be stored in the memory or executed by a second CPU that may be remotely located.
[0023] The software routines, when executed, transform the general purpose computer into a specific process computer that controls the chamber operation so that a chamber process is performed. For example, software routines may be used to precisely control the activation of the electronic control valves for the execution of process sequences according to embodiments described herein. Alternatively, the software routines may be performed in hardware, as an application specific integrated circuit or other type of hardware implementation, or a combination of software or hardware.
Copper Layer Formation
[0024] A method of forming a copper layer on a substrate is described. The copper layer is formed using a cyclic deposition technique.
[0025] FIG. 3 illustrates an embodiment of a cyclical deposition process sequence 300 according to the present invention detailing the various steps used for the formation of the copper layer utilizing a constant carrier gas flow. These steps may be performed in a process chamber similar to that described above with respect to FIG. 2.
[0026] As indicated in step 302, a substrate is provided to a process chamber.
The substrate may be for example, a silicon substrate having an interconnect pattern defined in one or more dielectric material layers formed thereon. The process chamber conditions such as, for example, the temperature and pressure are adjusted to enhance the adsorption of the process gases on the substrate. In general, for copper layer deposition, the process chamber should be maintained at a temperature less than about 180SC and a pressure within a range of about 1 torr to about 10 torr.
[0027] In one embodiment where a constant carrier gas flow is desired, a carrier gas stream is established within the process chamber, as indicated in step 304. Carrier gases may be selected so as to also act as a purge gas for the removal of volatile reactants and/or by-products from the process chamber. Carrier gases such as, for example, helium (He) and argon (Ar), and combinations thereof, among others may be used.
[0028] Referring to step 306, after the carrier gas stream is established within the process chamber, a pulse of a copper-containing precursor is added to the carrier gas stream. The term pulse as used herein refers to a dose of material added to the carrier gas stream. The pulse of the copper-containing precursor lasts for a predetermined interval. [0029] The time interval for the pulse of the copper-containing precursor is variable depending on 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 reactants used. For example, (1) a large-volume process chamber may lead to a longer time to stabilize the process conditions such as, for example, carrier purge gas flow and temperature, requiring a longer pulse time; (2) a lower flow rate for the process gas may also lead to a longer time to stabilize the process conditions, requiring a longer pulse time; and (3) a lower chamber pressure means that the process gas is evacuated from the process chamber more quickly, requiring a longer pulse time. In general, the process conditions are advantageously selected so that a pulse of the copper-containing precursor provides a sufficient amount of precursor so that at least a monolayer of the copper-containing precursor is adsorbed on the substrate. Thereafter, excess copper-containing precursor remaining in the chamber may be removed from the process chamber by the constant carrier gas stream in combination with the vacuum system.
[0030] In step 308, after the excess copper-containing precursor has been removed from the process chamber by the constant carrier gas stream, a pulse of a reducing gas is added to the carrier gas stream. The pulse of the reducing gas also lasts for a predetermined time interval that is variable as described above with reference to the copper-containing precursor. In general, the time interval for the pulse of the reducing gas should be long enough for adsorption of at least a monolayer of the reducing gas on the copper-containing precursor. Thereafter, excess reducing gas remaining in the chamber may be removed therefrom by the constant carrier gas stream in combination with the vacuum system.
[0031] Steps 304 through 308 comprise one embodiment of a deposition cycle for copper layer deposition. For such an embodiment, a constant flow of the carrier gas is provided to the process chamber modulated by alternating periods of pulsing and non-pulsing where the periods of pulsing alternate between the copper- containing precursor and the reducing gas along with the carrier gas stream, while the periods of non-pulsing include only the carrier gas stream. [0032] The time interval for each of the pulses of the copper-containing precursor and the reducing gas may have the same duration. That is, the duration of the pulse of the copper-containing precursor may be identical to the duration of the pulse of the reducing gas. For such an embodiment, a time interval (T for the pulse of the copper-containing precursor equals a time interval (T2) for the pulse of the reducing gas.
[0033] Alternatively, the time interval for each of the pulses of the copper- containing precursor and the reducing gas may have different durations. That is, the duration of the pulse of the copper-containing precursor may be shorter or longer than the duration of the pulse of the reducing gas. For such an embodiment, the time interval (Tt) for the pulse of the copper-containing precursor is different than the time interval (T2) for the pulse of the reducing gas.
[0034] In addition, the periods of non-pulsing between each of the pulses of the copper-containing precursor and the reducing gas may have the same duration. That is, the duration of the period of non-pulsing between each pulse of the copper- containing precursor and each pulse of the reducing gas may be identical. For such an embodiment, a time interval (T3) of non-pulsing between the pulse of the copper- containing precursor and the pulse of the reducing gas equals a time interval (T4) of non-pulsing between the pulse of the reducing gas and the pulse of the copper- containing precursor. During the time periods of non-pulsing only the constant carrier gas stream is provided to the process chamber.
[0035] Alternatively, the periods of non-pulsing between each of the pulses of the copper-containing precursor and the reducing gas may have different durations. That is, the duration of the period of non-pulsing between each pulse of the copper- containing precursor and each pulse of the reducing gas may be shorter or longer than the duration of the period of non-pulsing between each pulse of the reducing gas and the pulse of the copper-containing precursor. For such an embodiment, a time interval (T3) of non-pulsing between the pulse of the copper-containing precursor and the pulse of the reducing gas is different from a time interval (T4) of non-pulsing between the pulse of the reducing gas and the pulse of the copper-containing precursor. During the time periods of non-pulsing only the constant carrier gas stream is provided to the process chamber.
[0036] Additionally, the time intervals for each pulse of the copper-containing precursor, the reducing gas and the periods of non-pulsing therebetween for each deposition cycle may have the same duration. For such an embodiment, a time interval (T for the pulse of the copper-containing precursor, a time interval (T2) for the pulse of the reducing gas, a time interval (T3) of non-pulsing between the pulse of the copper-containing precursor and the pulse of the reducing gas and a time interval (T4) of non-pulsing between the pulse of the reducing gas and the pulse of the copper-containing precursor each have the same value for each deposition cycle. For example, in a first deposition cycle (d ), a time interval (TO for the pulse of the copper-containing precursor has the same duration as the time interval (Ti) for the pulse of the copper-containing precursor in subsequent deposition cycles (C2...CN). Similarly, the duration of each pulse of the reducing gas as well as the periods of non-pulsing between the pulse of the copper-containing precursor and the reducing gas in the first deposition cycle (d) is the same as the duration of each pulse of the reducing gas and the periods of non-pulsing between the pulse of the copper- containing precursor and the reducing gas in subsequent deposition cycles (C2...CN), respectively.
[0037] Alternatively, the time intervals for at least one pulse of the copper- containing precursor, the reducing gas and the periods of non-pulsing therebetween for one or more of the deposition cycles of the copper layer may have different durations. For such an embodiment, one or more of the time intervals (T for the copper-containing precursor, the time intervals (T2) for the reducing gas, the time intervals (T3) of non-pulsing between the pulse of the copper-containing precursor and the pulse of the reducing gas and the time intervals (T4) of non-pulsing between the pulse of the reducing gas and the pulse of the copper-containing precursor may have different values for one or more deposition cycles of the cyclical deposition process. For example, in a first deposition cycle (CO, the time interval (TO for the pulse of the copper-containing precursor may be longer or shorter than the time interval (TO for the pulse of the copper-containing precursor in subsequent deposition cycles (C2...CN). Similarly, the duration of each pulse of the reducing gas and the periods of non-pulsing between the pulse of the copper-containing precursor and the reducing gas in the first deposition cycle (CO may be the same or different than the duration of corresponding pulses of the reducing gas and periods of non-pulsing between the pulse of the copper-containing precursor and the reducing gas in subsequent deposition cycles (C2...CN), respectively.
[0038] Referring to step 310, after each deposition cycle (steps 304 through 308) a thickness of the copper will be formed on the substrate. Depending on specific device requirements, subsequent deposition cycles may be needed to achieve a desired thickness. As such, steps 304 through 308 are repeated until the desired thickness for the copper layer is achieved. Thereafter, when the desired thickness for the copper layer is achieved the process is stopped as indicated by step 212.
[0039] In an alternate process sequence described with respect to FIG. 4, the copper layer deposition cycle comprises separate pulses for each of the copper- containing precursor, the reducing gas and a purge gas. For such an embodiment, a copper layer deposition sequence 400 includes providing a substrate to the process chamber and adjusting the process chamber conditions (step 402), providing a first pulse of a purge gas to the process chamber (step 404), providing a pulse of a copper-containing precursor to the process chamber (step 406), providing a second pulse of a purge gas to the process chamber (step 408), providing a pulse of a reducing gas to the process chamber (step 410), and then repeating steps 404 through 410, or stopping the deposition process (step 414) depending on whether a desired thickness for the copper layer has been achieved (step 412).
[0040] The time intervals for each of the pulses of the copper-containing precursor, the reducing gas and the purge gas may have the same or different durations as discussed above with respect to FIG. 3. Alternatively, corresponding time intervals for one or more pulses of the copper-containing precursor, the reducing gas and the purge gas in one or more of the deposition cycles of the copper layer deposition process may have different durations. [0041] In FIGS. 3-4, the copper layer deposition cycle is depicted as beginning with a pulse of the copper-containing precursor followed by a pulse of the reducing gas. Alternatively, the copper layer deposition cycle may start with a pulse of the reducing gas followed by a pulse of the copper-containing precursor.
[0042] The copper-containing precursor may comprise an organometallic copper complex such as, for example, copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper"1"2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2, among others. Suitable reducing gases may include for example, silane (SiH4), disilane (S-2H6), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC2H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B4H12), pentaborane (B5H15), hexaborane (B6Hι8), heptaborane (B7H2ι), octaborane (B8H24), nanoborane (B9H27) and decaborane (B10H30), among others.
[0043] One exemplary process of depositing a copper layer comprises sequentially providing pulses of copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)) and pulses of diborane (B2H6). The copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS) may be provided to an appropriate flow control valve, for example, an electronic control valve, at a flow rate of between about 0.01 seem (standard cubic centimeters per minute) and about 5 seem, preferably between about 0.1 seem and about 1 seem, and thereafter pulsed for about 5 seconds or less, preferably about 1 second or less. The diborane (B H6) may be provided to an appropriate flow control valve, for example, an electronic flow control valve, at a flow rate of between about 1 seem to about 80 seem, preferably between about 10 seem and about 50 seem, and thereafter pulsed for about 10 seconds or less, preferably about 2 seconds or less. The substrate may be maintained at a temperature less than about 180 °C, preferably about 120 °C at a chamber pressure between about 0.1 torr to about 10 torr, preferably about 1 torr.
[0044] Another exemplary process of depositing a copper layer comprises sequentially providing pulses of copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)) and pulses of silane (SiH4). The copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS) may be provided to an appropriate flow control valve, for example, an electronic control valve, at a flow rate of between about 0.1 seem (standard cubic centimeters per minute) and about 5 seem, preferably between about 0.1 seem and about 1 seem, and thereafter pulsed for about 5 seconds or less, preferably about 1 second or less. The silane (SiH4) may be provided to an appropriate flow control valve, for example, an electronic flow control valve, at a flow rate of between about 1 seem to about 100 seem, preferably between about 10 seem and about 50 seem, and thereafter pulsed for about 10 seconds or less, preferably about 2 seconds or less. The substrate may be maintained at a temperature less than about 180 °C, preferably about 120 °C at a chamber pressure between about 0.1 torr to about 10 torr, preferably about 1 torr.
Formation of Copper Interconnects
[0045] FIGS. 5A-5B illustrate cross-sectional views of a substrate at different stages of a copper interconnect fabrication sequence incorporating the copper layer of the present invention. FIG. 5A, for example, illustrates a cross-sectional view of a substrate 500 having metal contacts 504 and a dielectric layer 502 formed thereon. The substrate 500 may comprise a semiconductor material such as, for example, silicon (Si), germanium (Ge), or gallium arsenide (GaAs). The dielectric layer 502 may comprise an insulating material such as, for example, silicon oxide or silicon nitride, among others. The metal contacts 504 may comprise for example, copper (Cu), among others. Apertures 504H may be defined in the dielectric layer 502 to provide openings over the metal contacts 504. The apertures 504H may be defined in the dielectric layer 502 using conventional lithography and etching techniques.
[0046] A barrier layer 506 may be formed in the apertures 504H defined in the dielectric layer 502. The barrier layer 506 may include one of more refractory metal- containing layers such as, for example, titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN), tantalum suicide nitride and titanium suicide nitride, among others. The barrier layer 506 may be formed using a suitable deposition process. For example, titanium nitride (TiN) may be deposited with a chemical vapor deposition (CVD) process from a reaction of titanium tetraehloride (TiCI4) and ammonia (NH3). Titanium suicide nitride (TiSiN) may be deposited by forming a titanium nitride (TiN) layer via thermal decomposition of tetrakis(dimethylamido) titanium (TDMAT) followed by exposure to silane (SiH4).
[0047] Thereafter, referring to FIG. 5B, the apertures 504H may be filled with copper (Cu) metallization to complete the copper interconnect. The copper metallization is formed using the cyclical deposition techniques described above with respect to FIGS. 3-4.
[0048] While foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

What is claimed is:
1. A method of forming a copper layer on a substrate, comprising:
(a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles and wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas.
2. The method of claim 1 wherein the period of exposure to the copper- containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration.
3. The method of claim 1 wherein at least one of the period of exposure the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration.
4. The method of claim 1 wherein the period of exposure to the copper- containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
5. The method of claim 1 wherein at least one period of exposure to the copper- containing precursor for one or more deposition cycle of the cyclical deposition process has a different duration.
6. The method of claim 1 wherein the period of exposure to the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
7. The method of claim 1 wherein at least one period of exposure to the reducing gas for one or more deposition cycle of the cyclical deposition process has a different duration.
8. The method of claim 1 wherein a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
9. The method of claim 1 wherein at least one period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has a different duration.
10. The method of claim 1 wherein a period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
11. The method of claim 1 wherein at least one period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor for one or more deposition cycles of the cyclical deposition process has a different duration.
12. The method of claim 1 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper""2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
13. The method of claim 1 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH4), disilane (S-2H6), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC2H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B4H12), pentaborane (B5H15), hexaborane (B6Hι8), heptaborane (B7H2O. octaborane (B8H24), nanoborane (B9H27) and decaborane
14. The method of claim 1 wherein the process chamber is maintained at a temperature less than about 180 °C.
15. A method of forming a copper layer on a substrate, comprising:
(a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas, wherein the period of exposure to the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper- containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration.
16. The method of claim 15 wherein the period of exposure to the copper- containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
17. The method of claim 15 wherein at least one period of exposure to the copper- containing precursor for one or more deposition cycle of the cyclical deposition process has a different duration.
18. The method of claim 15 wherein the period of exposure to the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
19. The method of claim 15 wherein at least one period of exposure to the reducing gas for one or more deposition cycle of the cyclical deposition process has a different duration.
20. The method of claim 15 wherein a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
21. The method of claim 15 wherein at least one period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has a different duration.
22. The method of claim 15 wherein a period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
23. The method of claim 15 wherein at least one period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor for one or more deposition cycles of the cyclical deposition process has a different duration.
24. The method of claim 15 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper+2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
25. The method of claim 15 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH ), disilane (S-2H6), dimethylsilane (SiC H8), methyl silane (SiCH6), ethylsilane (SiC H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B4H12), pentaborane (B5H15), hexaborane (B6H18), heptaborane (B7H21), octaborane (B8H24), nanoborane (B9H27) and decaborane (Bι0H30).
26. The method of claim 15 wherein the process chamber is maintained at a temperature less than about 180 °C.
27. A method of forming a copper layer on a substrate, comprising:
(a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas, and wherein at least one of the period of exposure the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration.
28. The method of claim 27 wherein the period of exposure to the copper- containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
29. The method of claim 27 wherein at least one period of exposure to the copper-containing precursor for one or more deposition cycle of the cyclical deposition process has a different duration.
30. The method of claim 27 wherein the period of exposure to the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
31. The method of claim 27 wherein at least one period of exposure to the reducing gas for one or more deposition cycle of the cyclical deposition process has a different duration.
32. The method of claim 27 wherein a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
33. The method of claim 27 wherein at least one period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has a different duration.
34. The method of claim 27 wherein a period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
35. The method of claim 27 wherein at least one period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor for one or more deposition cycles of the cyclical deposition process has a different duration.
36. The method of claim 27 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper*"2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
37. The method of claim 27 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH4), disilane (Si2He), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B4H12), pentaborane (B5H15), hexaborane (B6Hι8), heptaborane (B7H21), octaborane (B8H24), nanoborane (B9H27) and decaborane (Bι0H30).
38. The method of claim 27 wherein the process chamber is maintained at a temperature less than about 180 °C.
39. A method of forming a copper layer on a substrate, comprising: (a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas, wherein the period of exposure to the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper- containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration and wherein the period of exposure to the reducing gas, the period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and the period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration during each deposition cycle of the cyclical deposition process.
40. The method of claim 39 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1 (β-diketonate)silylolef in complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper*2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
41. The method of claim 39 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH4), disilane (S-2H6), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC2H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B H1 ), pentaborane (B5H15), hexaborane (B6Hι8), heptaborane (B7H20, octaborane (B8H24), nanoborane (B9H27) and decaborane (BιoH3o).
42. The method of claim 39 wherein the process chamber is maintained at a temperature less than about 180 °C.
43. A method of forming a copper layer on a substrate, comprising:
(a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas, wherein the period of exposure to the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper- containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration and wherein at least one period of exposure to the reducing gas, the period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and the period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration during one or more deposition cycles of the cyclical deposition process.
44. The method of claim 43 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1 (β-diketonate)silylolef in complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper+2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
45. The method of claim 43 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH ), disilane (Si2H6), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC2H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B H12), pentaborane (B5H15), hexaborane (B6Hι8), heptaborane (B7H21). octaborane (B8H24). nanoborane (B9H27) and decaborane (Bι0H30).
46. The method of claim 43 wherein the process chamber is maintained at a temperature less than about 180 °C.
47. A method of forming a copper layer on a substrate, comprising:
(a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas, wherein at least one of the period of exposure the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration, and the period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration during each deposition cycle of the cyclical deposition process.
48. The method of claim 47 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper"1"2 hexafluoroacetylacetonate (Cu+ (hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
49. The method of claim 47 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH4), disilane (S-2H6), dimethylsilane (SiC H8), methyl silane (SiCH6), ethylsilane (SiC H8), borane (BH3), diborane (B H6), triborane (B3H9), tetraborane (B4H12), pentaborane (B5H15), hexaborane (B6H18), heptaborane (B7H21), octaborane (B8H24), nanoborane (B9H27) and decaborane (B10H30).
50. The method of claim 47 wherein the process chamber is maintained at a temperature less than about 180 °C.
51. A method of forming a copper layer on a substrate, comprising:
(a) providing a substrate to a process chamber; and
(b) forming a copper layer on the substrate using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas, wherein at least one of the period of exposure the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration, and wherein at least one period of exposure to the reducing gas, the period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and the period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration during one or more deposition cycles of the cyclical deposition process
52. The method of claim 51 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper"1"2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
53. The method of claim 51 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH ), disilane (S.2H6), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC2H8), borane (BH3), diborane (B2H6), triborane (B3Hg), tetraborane (B4H12), pentaborane (B5H15), hexaborane (B6Hι8), heptaborane (B7H21). octaborane (B8H24), nanoborane (B9H27) and decaborane (B10H3o).
54. The method of claim 51 wherein the process chamber is maintained at a temperature less than about 180 °C.
55. A method of forming an interconnect structure, comprising:
(a) providing a substrate structure to a process chamber, wherein the substrate structure includes an insulating material layer having vias defined therethrough to an electrode; and
(b) forming a copper layer on the electrode using a cyclical deposition process, wherein the cyclical deposition process includes a plurality of cycles and wherein each cycle comprises establishing a flow of an inert gas in the process chamber and modulating the flow of the inert gas with alternating periods of exposure to one of a copper-containing precursor and a reducing gas.
56. The method of claim 55 wherein the period of exposure to the copper- containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor each have the same duration.
57. The method of claim 55 wherein at least one of the period of exposure the copper-containing precursor, the period of exposure to the reducing gas, a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the period of exposure to the reducing gas, and a period of flow of the inert gas between the period of exposure to the reducing gas and the period of exposure to the copper-containing precursor has a different duration.
58. The method of claim 55 wherein the period of exposure to the copper- containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
- 24 -
/
59. The method of claim 55 wherein at least one period of exposure to the copper-containing precursor for one or more deposition cycle of the cyclical deposition process has a different duration.
60. The method of claim 55 wherein the period of exposure to the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
61. The method of claim 55 wherein at least one period of exposure to the reducing gas for one or more deposition cycle of the cyclical deposition process has a different duration.
62. The method of claim 55 wherein a period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has the same duration.
63. The method of claim 55 wherein at least one period of flow of the inert gas between the period of exposure to the copper-containing precursor and the reducing gas during each deposition cycle of the cyclical deposition process has a different duration.
64. The method of claim 55 wherein a period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor during each deposition cycle of the cyclical deposition process has the same duration.
65. The method of claim 55 wherein at least one period of flow of the inert gas between the period of exposure to the reducing gas and the copper-containing precursor for one or more deposition cycles of the cyclical deposition process has a different duration.
66. The method of claim 55 wherein the copper-containing precursor comprises a material selected from the group consisting of copper +1(β-diketonate)silylolefin complexes including copper +1 hexafluoroacetylacetonate trimethylvinylsilane (Cu+1(hfac)(TMVS)), copper+2 hexafluoroacetylacetonate (Cu+2(hfac)2), copper +2 diacetylacetonate (Cu+2(acac)2) and 2Cu Me2NsiMe2CH2CH2SiNMe2.
67. The method of claim 55 wherein the reducing gas comprises one or more gases selected from the group consisting of silane (SiH4), disilane (Si2H6), dimethylsilane (SiC2H8), methyl silane (SiCH6), ethylsilane (SiC2H8), borane (BH3), diborane (B2H6), triborane (B3H9), tetraborane (B4Hι2), pentaborane (B5H15), hexaborane (B6H18), heptaborane (B7H20, octaborane (B8H24), nanoborane (B9H27) and decaborane (B10H30).
68. The method of claim 55 wherein the process chamber is maintained at a temperature less than about 180 °C.
PCT/US2003/017367 2002-06-04 2003-06-02 Deposition of copper films WO2003102266A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN03817559.2A CN1671883B (en) 2002-06-04 2003-06-02 Deposition of copper films
JP2004510498A JP2005528808A (en) 2002-06-04 2003-06-02 Copper film deposition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US38571502P 2002-06-04 2002-06-04
US60/385,715 2002-06-04
US10/441,242 2003-05-19
US10/441,242 US20040009665A1 (en) 2002-06-04 2003-05-19 Deposition of copper films

Publications (1)

Publication Number Publication Date
WO2003102266A1 true WO2003102266A1 (en) 2003-12-11

Family

ID=29715381

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/017367 WO2003102266A1 (en) 2002-06-04 2003-06-02 Deposition of copper films

Country Status (4)

Country Link
US (1) US20040009665A1 (en)
JP (1) JP2005528808A (en)
CN (1) CN1671883B (en)
WO (1) WO2003102266A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008510076A (en) * 2004-08-16 2008-04-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Atomic layer deposition of copper using surface activators.

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7049226B2 (en) * 2001-09-26 2006-05-23 Applied Materials, Inc. Integration of ALD tantalum nitride for copper metallization
US7204886B2 (en) * 2002-11-14 2007-04-17 Applied Materials, Inc. Apparatus and method for hybrid chemical processing
US7780785B2 (en) * 2001-10-26 2010-08-24 Applied Materials, Inc. Gas delivery apparatus for atomic layer deposition
US6911391B2 (en) * 2002-01-26 2005-06-28 Applied Materials, Inc. Integration of titanium and titanium nitride layers
US6972267B2 (en) * 2002-03-04 2005-12-06 Applied Materials, Inc. Sequential deposition of tantalum nitride using a tantalum-containing precursor and a nitrogen-containing precursor
JP4601975B2 (en) * 2004-03-01 2010-12-22 東京エレクトロン株式会社 Deposition method
US20090098290A1 (en) * 2004-09-27 2009-04-16 Mikio Watanabe Process for formation of copper-containing films
JP4934595B2 (en) 2005-01-18 2012-05-16 エーエスエム アメリカ インコーポレイテッド Reactor for thin film growth
JP5151082B2 (en) * 2006-07-20 2013-02-27 東京エレクトロン株式会社 Film forming method, film forming apparatus, and storage medium
JP5208128B2 (en) * 2007-12-04 2013-06-12 フルテック株式会社 Pressurized gas pulse control processing method and pressurized gas pulse control processing apparatus
US20120164449A1 (en) * 2010-12-23 2012-06-28 Stephen Woodrow Foss Fibers with improving anti-microbial performance
US10276411B2 (en) 2017-08-18 2019-04-30 Applied Materials, Inc. High pressure and high temperature anneal chamber
US10872804B2 (en) 2017-11-03 2020-12-22 Asm Ip Holding B.V. Apparatus and methods for isolating a reaction chamber from a loading chamber resulting in reduced contamination
US10872803B2 (en) 2017-11-03 2020-12-22 Asm Ip Holding B.V. Apparatus and methods for isolating a reaction chamber from a loading chamber resulting in reduced contamination
EP3768874A4 (en) 2018-03-19 2022-03-30 Applied Materials, Inc. Methods for depositing coatings on aerospace components
WO2019209401A1 (en) 2018-04-27 2019-10-31 Applied Materials, Inc. Protection of components from corrosion
US11009339B2 (en) 2018-08-23 2021-05-18 Applied Materials, Inc. Measurement of thickness of thermal barrier coatings using 3D imaging and surface subtraction methods for objects with complex geometries
WO2020219332A1 (en) 2019-04-26 2020-10-29 Applied Materials, Inc. Methods of protecting aerospace components against corrosion and oxidation
US11794382B2 (en) 2019-05-16 2023-10-24 Applied Materials, Inc. Methods for depositing anti-coking protective coatings on aerospace components
US11697879B2 (en) 2019-06-14 2023-07-11 Applied Materials, Inc. Methods for depositing sacrificial coatings on aerospace components
US11466364B2 (en) 2019-09-06 2022-10-11 Applied Materials, Inc. Methods for forming protective coatings containing crystallized aluminum oxide
US11519066B2 (en) 2020-05-21 2022-12-06 Applied Materials, Inc. Nitride protective coatings on aerospace components and methods for making the same
WO2022005696A1 (en) 2020-07-03 2022-01-06 Applied Materials, Inc. Methods for refurbishing aerospace components

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1142894A2 (en) * 2000-04-03 2001-10-10 Air Products And Chemicals, Inc. Volatile precursors for deposition of metals and metal-containing films
WO2003044242A2 (en) * 2001-11-16 2003-05-30 Applied Materials, Inc. Atomic layer deposition of copper using a reducing gas and non-fluorinated copper precursors

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430520A (en) * 1945-03-06 1947-11-11 Glass Science Inc Deposition of metal on glass from metal formates
US6482262B1 (en) * 1959-10-10 2002-11-19 Asm Microchemistry Oy Deposition of transition metal carbides
US3356527A (en) * 1964-04-23 1967-12-05 Ross W Moshier Vapor-plating metals from fluorocarbon keto metal compounds
US3482740A (en) * 1968-01-08 1969-12-09 Frank M Evans Cleaning and waxing appliances
US3594216A (en) * 1969-06-19 1971-07-20 Westinghouse Electric Corp Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate
JPH01313927A (en) * 1988-06-14 1989-12-19 Fujitsu Ltd Compound-semiconductor crystal growth method
US5273775A (en) * 1990-09-12 1993-12-28 Air Products And Chemicals, Inc. Process for selectively depositing copper aluminum alloy onto a substrate
US5098516A (en) * 1990-12-31 1992-03-24 Air Products And Chemicals, Inc. Processes for the chemical vapor deposition of copper and etching of copper
US5085731A (en) * 1991-02-04 1992-02-04 Air Products And Chemicals, Inc. Volatile liquid precursors for the chemical vapor deposition of copper
CA2082771C (en) * 1992-11-12 1998-02-10 Vu Quoc Ho Method for forming interconnect structures for integrated circuits
US5322712A (en) * 1993-05-18 1994-06-21 Air Products And Chemicals, Inc. Process for improved quality of CVD copper films
US5464666A (en) * 1995-02-06 1995-11-07 Air Products And Chemicals, Inc. Process for chemical vapor codeposition of copper and aluminum alloys
US6891269B1 (en) * 1995-07-05 2005-05-10 Fujitsu Limited Embedded electroconductive layer structure
US5736192A (en) * 1995-07-05 1998-04-07 Fujitsu Limited Embedded electroconductive layer and method for formation thereof
US6342277B1 (en) * 1996-08-16 2002-01-29 Licensee For Microelectronics: Asm America, Inc. Sequential chemical vapor deposition
US5916365A (en) * 1996-08-16 1999-06-29 Sherman; Arthur Sequential chemical vapor deposition
JPH10189493A (en) * 1996-10-29 1998-07-21 Nippon Steel Corp Deposition of metal film
KR100261017B1 (en) * 1997-08-19 2000-08-01 윤종용 Method for forming metal wiring of semiconductor device
KR100287180B1 (en) * 1998-09-17 2001-04-16 윤종용 Method for manufacturing semiconductor device including metal interconnection formed using interface control layer
US6305314B1 (en) * 1999-03-11 2001-10-23 Genvs, Inc. Apparatus and concept for minimizing parasitic chemical vapor deposition during atomic layer deposition
US6200893B1 (en) * 1999-03-11 2001-03-13 Genus, Inc Radical-assisted sequential CVD
US6613383B1 (en) * 1999-06-21 2003-09-02 Regents Of The University Of Colorado Atomic layer controlled deposition on particle surfaces
US6391785B1 (en) * 1999-08-24 2002-05-21 Interuniversitair Microelektronica Centrum (Imec) Method for bottomless deposition of barrier layers in integrated circuit metallization schemes
US6203613B1 (en) * 1999-10-19 2001-03-20 International Business Machines Corporation Atomic layer deposition with nitrate containing precursors
FI20000099A0 (en) * 2000-01-18 2000-01-18 Asm Microchemistry Ltd A method for growing thin metal films
WO2001066832A2 (en) * 2000-03-07 2001-09-13 Asm America, Inc. Graded thin films
US6482733B2 (en) * 2000-05-15 2002-11-19 Asm Microchemistry Oy Protective layers prior to alternating layer deposition
US6679951B2 (en) * 2000-05-15 2004-01-20 Asm Intenational N.V. Metal anneal with oxidation prevention
US6759325B2 (en) * 2000-05-15 2004-07-06 Asm Microchemistry Oy Sealing porous structures
JP5173101B2 (en) * 2000-05-15 2013-03-27 エイエスエム インターナショナル エヌ．ヴェー． Integrated circuit manufacturing method
US6878628B2 (en) * 2000-05-15 2005-04-12 Asm International Nv In situ reduction of copper oxide prior to silicon carbide deposition
EP1340269B1 (en) * 2000-11-30 2009-02-25 Asm International N.V. Thin films for magnetic devices
US6949450B2 (en) * 2000-12-06 2005-09-27 Novellus Systems, Inc. Method for integrated in-situ cleaning and subsequent atomic layer deposition within a single processing chamber
US20020197402A1 (en) * 2000-12-06 2002-12-26 Chiang Tony P. System for depositing a film by modulated ion-induced atomic layer deposition (MII-ALD)
KR100386034B1 (en) * 2000-12-06 2003-06-02 에이에스엠 마이크로케미스트리 리미티드 Method of Fabricating Semiconductor Device Employing Copper Interconnect Structure Having Diffusion Barrier Stuffed with Metal Oxide
US20020104481A1 (en) * 2000-12-06 2002-08-08 Chiang Tony P. System and method for modulated ion-induced atomic layer deposition (MII-ALD)
US6428859B1 (en) * 2000-12-06 2002-08-06 Angstron Systems, Inc. Sequential method for depositing a film by modulated ion-induced atomic layer deposition (MII-ALD)
US20020073924A1 (en) * 2000-12-15 2002-06-20 Chiang Tony P. Gas introduction system for a reactor
US20020076481A1 (en) * 2000-12-15 2002-06-20 Chiang Tony P. Chamber pressure state-based control for a reactor
US6630201B2 (en) * 2001-04-05 2003-10-07 Angstron Systems, Inc. Adsorption process for atomic layer deposition
US20020076507A1 (en) * 2000-12-15 2002-06-20 Chiang Tony P. Process sequence for atomic layer deposition
US20020127336A1 (en) * 2001-01-16 2002-09-12 Applied Materials, Inc. Method for growing thin films by catalytic enhancement
US6811814B2 (en) * 2001-01-16 2004-11-02 Applied Materials, Inc. Method for growing thin films by catalytic enhancement
US6464779B1 (en) * 2001-01-19 2002-10-15 Novellus Systems, Inc. Copper atomic layer chemical vapor desposition
US7348042B2 (en) * 2001-03-19 2008-03-25 Novellus Systems, Inc. Continuous method for depositing a film by modulated ion-induced atomic layer deposition (MII-ALD)
US20020144655A1 (en) * 2001-04-05 2002-10-10 Chiang Tony P. Gas valve system for a reactor
US20020144657A1 (en) * 2001-04-05 2002-10-10 Chiang Tony P. ALD reactor employing electrostatic chuck
US20030042630A1 (en) * 2001-09-05 2003-03-06 Babcoke Jason E. Bubbler for gas delivery
JP4938962B2 (en) * 2001-09-14 2012-05-23 エーエスエム インターナショナル エヌ．ヴェー． Metal nitride deposition by ALD using gettering reactant
US6657406B2 (en) * 2001-09-19 2003-12-02 Delphi Technologies, Inc. Soft start control method for a motor-driven actuator
US20030064153A1 (en) * 2001-10-01 2003-04-03 Rajendra Solanki Method of depositing a metallic film on a substrate
US6960537B2 (en) * 2001-10-02 2005-11-01 Asm America, Inc. Incorporation of nitrogen into high k dielectric film
US6620956B2 (en) * 2001-11-16 2003-09-16 Applied Materials, Inc. Nitrogen analogs of copper II β-diketonates as source reagents for semiconductor processing
JP2005520053A (en) * 2002-01-18 2005-07-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Volatile copper (II) complexes for depositing copper thin films by atomic layer deposition
US6824816B2 (en) * 2002-01-29 2004-11-30 Asm International N.V. Process for producing metal thin films by ALD
TWI230544B (en) * 2002-07-25 2005-04-01 Veutron Corp Light source control method and apparatus of image scanner

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1142894A2 (en) * 2000-04-03 2001-10-10 Air Products And Chemicals, Inc. Volatile precursors for deposition of metals and metal-containing films
WO2003044242A2 (en) * 2001-11-16 2003-05-30 Applied Materials, Inc. Atomic layer deposition of copper using a reducing gas and non-fluorinated copper precursors

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MARTENSSON P ET AL: "ATOMIC LAYER EPITAXY OF COPPER. GROWTH AND SELECTIVITY IN THE CU(II)-2,2,6,6-TETRAMETHYL-3,5-HEPTANEDIONATE/H2 PROCESS", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, ELECTROCHEMICAL SOCIETY. MANCHESTER, NEW HAMPSHIRE, US, vol. 145, no. 8, August 1998 (1998-08-01), pages 2926 - 2931, XP000929578, ISSN: 0013-4651 *
SOLANKI R ET AL: "Atomic layer deposition of copper seed layers", ELECTROCHEMICAL AND SOLID-STATE LETTERS, OCT. 2000, ELECTROCHEM. SOC, USA, vol. 3, no. 10, pages 479 - 480, XP002254875, ISSN: 1099-0062 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008510076A (en) * 2004-08-16 2008-04-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Atomic layer deposition of copper using surface activators.

Also Published As

Publication number Publication date
US20040009665A1 (en) 2004-01-15
CN1671883B (en) 2011-12-21
CN1671883A (en) 2005-09-21
JP2005528808A (en) 2005-09-22

Similar Documents

Publication Publication Date Title
US7041335B2 (en) Titanium tantalum nitride silicide layer
US7404985B2 (en) Noble metal layer formation for copper film deposition
US20040009665A1 (en) Deposition of copper films
US20040009336A1 (en) Titanium silicon nitride (TISIN) barrier layer for copper diffusion
US7244683B2 (en) Integration of ALD/CVD barriers with porous low k materials
US7262133B2 (en) Enhancement of copper line reliability using thin ALD tan film to cap the copper line
US11587829B2 (en) Doping control of metal nitride films
US6939804B2 (en) Formation of composite tungsten films
US6727169B1 (en) Method of making conformal lining layers for damascene metallization
US6720027B2 (en) Cyclical deposition of a variable content titanium silicon nitride layer
US20030124262A1 (en) Integration of ALD tantalum nitride and alpha-phase tantalum for copper metallization application
US7279432B2 (en) System and method for forming an integrated barrier layer
US7211508B2 (en) Atomic layer deposition of tantalum based barrier materials
US20030203616A1 (en) Atomic layer deposition of tungsten barrier layers using tungsten carbonyls and boranes for copper metallization
US20100151676A1 (en) Densification process for titanium nitride layer for submicron applications
EP1221177A1 (en) Conformal lining layers for damascene metallization
WO2013082370A1 (en) Doped tantalum nitride for copper barrier applications
WO2003038892A2 (en) Atomic-layer-deposited tantalum nitride and alpha-phase tantalum as barrier layers for copper metallization
KR20050016511A (en) Deposition of copper films

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR

WWE Wipo information: entry into national phase

Ref document number: 1020047019740

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2004510498

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 20038175592

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020047019740

Country of ref document: KR