CA2058483C - Process for the chemical vapor deposition of copper - Google Patents
Process for the chemical vapor deposition of copperInfo
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- CA2058483C CA2058483C CA002058483A CA2058483A CA2058483C CA 2058483 C CA2058483 C CA 2058483C CA 002058483 A CA002058483 A CA 002058483A CA 2058483 A CA2058483 A CA 2058483A CA 2058483 C CA2058483 C CA 2058483C
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
- H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
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- 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
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/12—Gaseous compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
Abstract
A process is provided for selectively depositing copper films on metallic or other electrically conducting portions of substrate surfaces by contacting the substrate at a temperature from 110° to 190°C with a volatile organometallic copper complex, in the gas phase, represented by the structural formula:
Description
PROCESS FOR THE CHEMICAL VAPOR DEPOSITION OF COPPER
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the deposition of copper films onto conducting metallic or metallic-like surfaces.
BACKGROUND OF THE INVENTION
In the electronics industry there is a steady trend towards manufacturing microprocessors of increasingly high speed and large information storage capacity.
This requires the individual electrical devices such as transi~ols, etc. within the microprocessors to be fabricated at an increasingly small scale. The metallic electrical interconnects between the devices also need to be miniaturized. As device and interconnect dimensions approach one-half to one-quarter of a micron, the choice of interconnect metal becomes critical. The large current densities resulting from small interconnect cross sectional areas can lead to major problems such as electromigration, stress migration, and voiding where the metal lines become fractured or otherwise physically degraded under operating conditions, a major drawback with aluminum alloys. Metal interconnects also need to provide the lowest electrical resistance path possible since resistance-capacitance delays become a dominant factor in circuitperformance at sub half micron levels. The alulllhlulll that is widely used in present day interconnect manufacturing is reasonably conductive (2.7 microohm cm), but needs to be alloyed with 0.5 to 4.0 atomic % Cu to ~"ini~"i~e the electromigration tendencies of the pure metal. Tungsten, also widely used, is electromigration resistant but is of higher resistivity (5.4 microohm cm). Considering these facts, copper should be an excellent interconnect metal as it is both highly conductive (1.7 microohm cm) and electromigration resistant.
k~
~,' 20s8~g3 Metall;c interconnects are typically horizontal lines (runners) or plugs (vias) that wire together devices in microprocessors. At feature sizes of >1 micron these metallic components can be built into the microcircuits by PVD (Physical Vapor Deposition) techniques such as sputtering or evaporation. In essence PVD consists of condensing a metal vapor onto a surface or into a hole or channel of a circuit where an electrical connection needs to be formed. Since this is a non-selective metallization, either a postdeposition clean-up (i.e. etch-back) or a predeposition masking of the substrate (i.e. the lift-off technique) is required in order to prepare individual discreet metal components. However, the severe surface topographies presented by sub-micron features preclude the effective use of PVD since this "line of sight" technique cannot provide a uniform conformal coating on such high aspect ratio highly convoluted surfaces. Specific examples of these shortcomings include the phenomena of geometrical shadowing and poor step coverage.
A superior process for producing these microscopic metal features is CVD
(Chemical Vapor Deposition). In this technique a volatile metal-organic compound in the gas phase is contacted with areas of a circuit where growth of a metal film (i.e. interconnect) is required. A surface catalyzed chemical reaction then occurs which leads to deposition of the desired metal. Since this is a chemical reaction, there is potential for it to provide surface selective metallization. That is, CVD metal deposition can be made to occur at only specific locations compared to the non-selective PVD processes. Also, since the metal film steadily grows on the desired surface it is of a uniform thickness and highly conformal even to severe geometries. In this respect CVD
is naturally suited to fabricating submicron high aspect ratio features.
An example of selective CVD metallization that is currently commercially practiced is the deposition of tungsten onto a silicon surface using tungsten hexaf1uoride as the volatile organometallic precursor(see T. Ohba, et al., "Tungsten and Other Advanced Metals for VLSI/ULSI Applications V," Ed. by S.
S. Wong and S. Furukawa, MRS, Pittsburgh, Pennsylvania, 273 (1990) ). The chemistry that drives this process can be divided into two steps. Initially the WF6 reacts with the elemental silicon surface to yield tungsten metal and volatile silicon hexafluoride. Hydrogen gas is then added to the system which 2(~8483 reduces further WF6 at the freshly formed metal surface thereby yielding additional tungsten and HF gas. Although this system currently enjoys widespread use as the only "selective" CVD metallization process that is widely commercially available, loss of selectivity can be observed and is commonly ascribed to the corrosive nature of HF. T. Ohba, et al., Tech. Dig.
IEDM, 213 (1987) teach the use of silane as a reducing agent for WF6 to achieve higher deposition rates while avoiding the production of HF gas.
Desirable selectivities for a copper CVD process include deposition onto conducting metallic or metallic like surfaces such as tungsten, tantalum or titanium nitride versus insulating surfaces such as silicon oxide. These metallic surfaces provide a diffusion barrier between the CVD copper and the underlying silicon substrate that the device is grown upon.
Copper films have previously been prepared via CVD using various copper precursors. Most of these compounds will only deposit copper metal at temperatures higher than 200~C with no significant selectivity between substrates such as diffusion barrier surfaces vs. silicon oxide. The best known and most frequently used CVD copper precursor is copper+2 bis(hexafluoroacetylacetonate). This highly fluorinated organometallic precursor is significantly more volatile than its parent unfluorinated complex copper+2 bis(acetylacetonate) and its ease of vaporization readily lends this compound towards CVD processes. The use of this compound as a general precursor for CVD copper metallization was first described by R. L. Van Hemert et al. J. Electrochem. Soc. (112), 1123 (1965) and by R. W. Moshier et al.
U. S. Patent 3,356,527. More recently Reisman, et al., J. Electrochemical Soc., Vol. 136, No. 11, November 1989 and A. E. Kaloyeros et al., Journal of Electronic Materials, Vol. 19, No. 3, 271 (1990) in two independent studies have also evaluated the use of this compound as a copper precursor for electronics applications. In these studies copper films were formed by contacting vapors of copper~2(hfac)2, mixed with either an inert gas (argon) or with hydrogen and contacting the mixture with a heated substrate surface.
In the case of using hydrogen the copper+2 atom in the precursor complex is formally reduced to copper metal while the hfac~l ligand becomes protonated to yield a neutral volatile compound. In the case of using an inert gas the copper+2(hfac)2 is simply pyrolyzed to give copper metal and fragments of the hfac ligand.
Pure copper is reported for the hydrogen reduction but oxygen and carbon are found in the films obtained by pyrolysis. However, the lowest deposition temperatures for either process is 250~C and no strong selectivities towards metallic vs. silicon oxide surfaces are reported. Copper films have also been prepared from copper+2(hfac)2 by plasma enhanced deposition, C. Oehr, H. Suhr, Appl. Phy. A. (45) 151-154 (1988),laser photothermal decomposition, F.A. Houle; C.R. Jones; T. Baum; C. Pico; C.A.Korae; Appl. Phys. Lett. (46) 204-206 (1985), and photochemical decomposition ofcopper+2(hfac)2 ethanol adducts, F.A. Houle; R.J. Wilson; T.H. Baum; J. Vac. Sci.
Technol. A (4), 2452-2458 (1986). Some of these methods yield fluorine cont~min~te~l films and none are reported to yield selective depositions. Similar hydrogen reduction of volatile copper compounds has also been demonstrated by Charles et al., U.S.
Patent 3,594,216 using copper+2 ~-ketoimine complexes at 400~C to deposit coppermetal films onto glass or quartz substrates. No mention of selectivity is made. G.S.
Girolami, et al., Chem. Mater. (1) 8-10 (1989) reported using copper+l t-butoxide to yield copper films CVD at 400~C, but the resultant films were hllpule in that they contained 5 atomic % oxygen.
The only CVD precursors known to deposit pure copper metal films below 200~C are the copper+l cyclopentadienyl phosphine compounds described by Beech et al., Chem. Mater. (2) 216-219 (1990), but these are also not reported to be strongly selective towards metallic or metallic like surfaces vs. silicon oxide or similar insulating dielectrics. An additional problem that this particular class of compounds faces for electronics applications is their potential to cont~min~te microcircuits with phosphorus, an element that is extensively used as a silicon dopant.
SUMMARY OF THE INVENTION
The present invention is an improved chemical vapor deposition process for selectively depositing pure, thin copper films on metallic or other electricallyconducting portions of a substrate surface. The improvement comprises contacting the substrate with a volatile organometallic copper complex having a vapor pressure greater than or equal to 0.01mm Hg at 100~C represented by the structural formula:
B
~n58483 O R2 () Cu+~ (Rl C-C-Il -R3) .L
where Rl and R3 are each independently C,-C8 perfluoroalkyl, R2 is H or Cl-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation.
This process provides for the selective deposition of pure copper films onto themetallic or other electrically conducting portions of a substrate surface at lowdeposition temperatures; i.e. from about 110~ to 190~C.
Additionally, it has been found that the deposition reaction can be reversed to cleanly and selectively etch deposited copper from a substrate surface. In this process, a substrate on which has been deposited a copper film is contacted with an organometallic copper complex and an olefin, CO or isonitrile, in the gas phase,represented by the structural formulae:
O R2 o CU+2 (Rl _ C -C -C -R3)2 + L2 where R', R2 and R3 are the same as above and L2 is the same as L defined above.
BRIEF DESCRIPTION OF THE DRAWINGS
The single Figure is a diagram of a conventional CVD apparatus used to carry out the process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
An improved chemical vapor deposition process has been developed for selectively depositing pure, thin copper films on metallic or other electricallyconducting portions of a substrate surface. The improvement comprises contacting the substrate with a volatile organometallic copper complex having a vapor pressure greater than or equal to 0.01mm Hg at 100~C. The copper complexes which are suitable for this deposition application can be represented by the structural formula:
C
i 2~5~83 O R2 o Cu+l (Rl _ C -C e -R3) ~L
where Rl and R3 are each independently Cl-C8 perfluoroalkyl, R2 is H or Cl-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation. In instances wherein L is an unsaturated hydrocarbon ligand, suitable examples include: ethylene, acetylene, l-octene, isobutylene, 1,5-cyclooctadiene, stilbene, diphenylacetylene, styrene, cyclooctene, 1,5,9-cyclododecatriene, 1,3-hexadiene, isopropylacetylene, l-decene, 2,5-bicycloheptadiene, l-octadecene, cyclopentene, octalin, methylene cyclohexane, diphenyl fulvene, l-octadecyne, benzyl cinnamate, benzal acetophenone, acrylonitrile, maleic anhydride, oleic acid, linolenic acid, acrylic acid, methyl methacrylate and diethyl maleate. Suitable isonitriles include methyl isocyanide, butyl ;socyanide, cyclohexyl isocyanide, phenylethyl isocyanide and phenyl isocyanide.
These compounds were originally disclosed in U. S. Patent 4,425,281 for use as complexing agents in a system of processes that separate carbon monoxide, alkenes or alkynes from various gas mixtures. Unexpectedly, we have found these compounds to be volatile compounds which, in their vapor form, can be used under certain conditions to selectively deposit copper metal films of high purity onto either metallic or other electrically conducting surfaces to the exclusion of deposition onto silicon oxide or other similar non-conducting (ie. insulating) surfaces. Such metallic or other electrically conducting surfaces include: W, TiN, Ta, Al, and the like. The deposition conditions are those typically employed in conventional copper CVD applications, with the exception that the present process allows for substantially lower deposition temperatures to be used, i.e., temperatures from about 110~ to 190~C, and preferably from 130~ to 180~C. While not intending to be bound by theory, the metallization process of the present invention is believed to occur via the following sequence of events:
a). Adsorbtion of the copper+l-olefin complex onto the surface(s) to be metallized 2 0 5 z~
b). surface catalyzed loss of olefin to yield an unstable copper+
species c). disproportionation of the unstable copper+l species to yield copper metal and a volatile copper+2 species.
This reaction mechanism is represented below for the complex copper+l(hfac)-COD where (s) indicates adsorbtion onto the surface and (g) indicates the compound in the gas phase (hfac being an abbreviation for the hexafluoroacetylacetonate anion and COD being an abbreviation for 1,5-cyclooctadiene). Both the COD and the Cu+2(hfac)2 are volatile byproducts.
1. 2Cu+l(hfac).COD(g) -----> 2Cu+l(hfac).COD(s) 2. 2Cu+l(hfac).COD(s) -----> 2Cu+l(hfac)(s) + 2COD(g) 3. 2Cu+l(hfac)(s) -----> Cu~(s) + Cu+2(hfac)2(g) The above described mechanism is unique in the field of CVD copper metallizat;on and offers a number of processing advantages. Stabilization of the +l oxidation state of copper is provided by coordination of an olefin and decomposition to copper metal is caused by loss of an olefin. Therefore, it is possible to control the copper deposition temperature, the rate of deposition and the resulting film morphology by increasing the concentration (i.e. pressure) of the olefin in the system or by adding different olefins.
Similarly, normally unstable volatile olefin complexes can be prepared by either using high pressures of olefin to stabilize copper+l and then effecting a CVD deposition by releasing the pressure or, using low temperatures and high olefin pressures to stabilize copper+l then effecting a copper deposition by warming and/or pressure drop.
The present process has the ability to selectively deposit copper films having small grain size at low temperatures, i.e., from 110~to 190~C, without significantly compromising the growth rate of the film. The small grain size of the deposited metal minimizes the need for post deposition planarization.
Additionally, the ability to deposit copper at these lower temperatures is especially important for the so called upper-level metals in multi-metal layer 20~483 ICs as excessive heat is to be avoided during the later stages of microprocessor fabrication to prevent thermally induced interdiffusion of of layer materials and dopants at device interfaces. Also, since useful deposition rates, appropriate grain size etc. can be accomplished below 200~C, standard photoresist materials can be used for patterning purposes via photolithographic techniques.
Additionally, the present process is advantageous in that it does not result in the release of corrosive or otherwise detrimental byproducts that can lead to a loss of selectivity or damage to the microprocessor substrate.
In an additional embodiment, hydrogen can be used in the CVD reduction of the organometallic copper complexes of the present invention, such as Cu+l(hfac)-olefin complexes, to yield metallic copper in a similar manner that it is reported to reduce Cu+2(hfac)2. This more effectively utilizes the precursor from the perspective that each metal center would yield metallic copper in contrast to the disproportionation reaction where only l/2 of the initial Cu+l centers yield copper metal. In instances in which this results in the loss of selectivity, an initial selective deposition in the absence of hydrogen can be utilized to deposit a seed layer of copper which would then be grown by subsequent CVD processing by hydrogen reduction. Optionally, other 20 reducing gases could also be used.
It has also been found that the present CVD reaction could be reversed such that copper metal deposited via a blanket deposition reaction could be removed, i.e., etched from the metallic surface area of a substrate. In accordance with this technique, a copper (+2) complex along with a suitable 25 olefin, both in the vapor phase, are brought into contact with a substrate onto which excess copper has been deposited. The copper metal on the surface of the substrate is converted into a volatile copper (+l) complex and is evaporated away from the metal. The general chemical equation for this etching reaction is as follows:
Cu~ + Cu+2(ligand)2 + 2 olefin > 2Cu+l(ligand)olefin Prior to the present invention, known etching processes were inappropriate for copper since prior processes resulted in the generation of copper halides 35 which are involatile and were left behind as surface contaminants.
2~5~83 g ExDerimental Synthesis:
In the following examples, temperatures are set forth uncorrected in degrees celcius. Unless otherwise noted, all parts and percentages are by weight. 1,1,1,5,5,5-hexafluoro-2,4-pentanedione was purchased from Fairfield Chemical Company (P.O. Box 20, Blythewood, SC 29106). 1,5-cyclooctadiene (i.e. COD), norbornadiene (i.e. NB), potassium hydride, copper+l oxide and copper+l chloride were purchased from Aldrich Chemical Co. (940 W. St. Paul Avenue, Milwaukee WI 53233). HPLC grade terahydrofuran (THF) and hexane were individually distilled from sodium benzophenone under an atmosphere of nitrogen prior to use. All operations in the preparation of metal complexes were carried out using standard Schlenk line techniques as described by D. F. Shriver in the "Manipulations of Air Sensitive Compounds" McGraw-Hill Publishing Co. Copper+l(hfac)-COD and [copper+l(hfac)]2-NB compounds, i.e. 1 and 2 respectively as shown in Table 1 were initially prepared by the method described by Doyle tOrganometallics, Vol. 4, No. 5, 830, (1985)]. This consisted of reacting cuprous oxide with one equivalent of hexafluoroacetylacetonate in THF solvent in the presence of one equivalent of olefin to yield the desired copper+l olefin complex and water, according to equation (1) shown below where the olefin is COD.
Cu20 + 2H-hfac + 2COD -----> 2Cu+l(hfac)-COD + H20 (1) However, we found that while this synthesis yielded the desired complex, it was heavily contaminated with Cu~2(hfac)2. Although Doyle claims that these complexes are moisture insensitive we have found during the course of our research that this is not so and that the presence of water leads to some of the copper+lolefin complex to decompose to copper+2 complex and copper, presumably via a disproportionation mechanism. This copper+2 contaminant then has to be removed via a series of recrystallizations and sublimations. To overcome this problem we developed a new "water free" synthesis where the potassium salt of hfac is reacted with cuprous chloride in THF solvent in the presence of one equivalent of olefin. This yields the desired copper olefin complex and potassium chloride by-product as shown below in equation 2:
2 0 ~ 3 K+ hfac~ + CuCl + olefin -----> Cu+l(hfac)-(olefin) + KCl (2) No Cu+2(hfac)2 was observed to form. ~e believe that this represents a generic route to any copper+l (~-diketonate).olefin complex. An example of 5 this route is shown below for the synthesis of copper+l(hfac)-COD:
Under a blanket of dry nitrogen 0.80g (2x10-2 moles) of potassium hydride are charged into a 100 ml Schlenk flask fitted with a rubber septum. 25 ml of dry tetrahydrofuran (THF) solvent are then added to the hydride via canula, the nitrogen atmosphere vented and 2.82 ml (4.16 g 2x10-2 moles) of hexafluoroacetylacetonate slowly added via syringe over a 10 minute period with stirring. A vigorous evolution of hydrogen is observed and stirring is continued until it ceases. A second nitrogen filled 100 ml Schlenk flask is charged with 1.98 g (2x10-2 moles) of cuprous chloride and 10 ml of dry THF
solvent are added into the flask along with the 2.54 ml (2x10-2 moles) of 15 1,5-cyclooctadiene. The initial potassium hexafluoroacetylacetonate solutionis then added via canula into the second flask with stirring. A bright yellow coloration is observed. After two hours of stirring at room temperature the solution is filtered under nitrogen to yield a clear yellow solution. The THF
is then evaporated to give an 80X yield of copper+l(hfac)-COD as a bright 20 yellow crystalline solid which can be further purified by recrystallization from dry hexane or sublimation at 65~C, 10-3 torr.
The selective metallizations of various substrates were performed using the apparatus shown in the accompanying figure. Under an atmosphere of nitrogen the source chamber 1 was loaded with 0.5-1.5 g of volatile copper+l hexafluoroacetylacetonate-olefin complex and then fitted to the precursor feed tube 3. Valve 5 was then closed. The susceptor 7 was then fitted with two silicon coupons 8 & 9, side by side, one bearing a silicon oxide surface and the other a metallized surface (i.e. TiN, Ta etc.). Alternatively, just one coupon bearing a silicon oxide/metal patterned surface (e.g. a W/SiO2 FLTC) was fitted to the susceptor. The entire susceptor assembly was then loaded into the deposition chamber 11 and a teflon stopper 12 was fitted in the top of the deposition chamber 11 through which a thermocouple 14 passes from the -~ 20384~3 susceptor 7 to a temperature controller, and a heater rod 16 passes from the temperature controller to the suscepter 7. A condensor 13 was then connected to deposition chamber 11 with valve 15 closed. A vacuum line 17 and two cold water lines 19 & 21 were then connected to condensor 13. Valves 5 and 15 were 5 then opened and the entire apparatus evacuated to 50 mtorr pressure. After a few minutes valve 5 is closed and the entire apparatus was lowered into a thermostated oil bath set at the desired source temperature up to the immersion line indicated. The thermostated heat for the susceptor was turned on and the susceptor allowed to reach the predetermined temperature (from 130-180~C). The apparatus was then left one hour or longer under vacuum (50 mtorr). The cooling water to the condensor was then turned on. After this time period valve 5 was opened thereby allowing vapors of the precursor to be drawn through the deposition chamber and to deposit a copper film on the susceptor and its mounted substrate(s). At the end of a run valve 5 was shut, the entire apparatus was backfilled with nitrogen gas and the susceptor assembly removed. Cu+2(hfac)2 was observed as sublimate collected onto the cold finger of the condensor along with unreacted Cu~hfac.olefin complex.
In Example 10 a similar piece of equipment was utilized to show that compound 1 could be vaporized at 105~C in a flow of dry nitrogen at one 20 atmosphere pressure and the resultant vapor passed over a silicon coupon at 150~C to yield a film of pure copper metal.
The results of these metallizations along with the specific complexes, substrates, and reaction conditions are listed in Table 1 below. Selectivity was determined by both visual inspection of the coupons at 200-lOOOX using an 25 optical microscope and by a scanning electron microscope (SEM) to determine the presence or absence of copper. The thickness of each deposited film was determined by viewing them edge on in SEM. The purity of the copper deposited was determined via Auger electron spectroscopy depth profiling. The purity of the copper films deposited onto TiN and Ta surfaces were measured from the metallized coupons used in runs 8 & 9 respectively. The purity of the copper film deposited onto tungsten was measured from the FLTC wafer used in run 2.
In all cases the purity of the copper was found to be >99.9Z with carbon, oxygen, and fluoride being below detectable limits.
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A run was carried out to demonstrate the ability to etch excess copper from the surface of a substrate. This process was demonstrated using Cu+2(hfac)2 along with l-tridecene as the olefin slnce the volatl1ities of both are comparable. 1.09 of Cu+2(hfac)2 was added to 3 ml of l-tridecene and the mixture heated to 60~C then cooled to room temperature. Some copper complex precipitated out and was discarded. The saturated solutlon of complex in l-tridecene was then heated to 120~C and 200 ml/min of nitrogen bubbled lo through it to produce a nitrogen/complex/olefin vapor mixture. This vapor was then passed over a copper covered surface heated to 120~C for one hour, resulting in an etching of the copper surface. The etched sample was a silicon coupon that had been covered sequentially with 5000~ of silicon oxide, 1200~ of tantalum and lOoOA of copper. The surface of the coupon was partially masked with polyimide tape such that only a narrow trench of copper was exposed to the etch vapors. Once the etch was completed, the tape was removed and the extent of the etch determined by measuring the depth of copper removed from the surface via a stylus profilometer. In this technique, a sapphire stylus point contacts and tracks across the surFace of the etched coupon and directly measures ;ts surface topography in units of Angstroms. In addition, the etched surface was also examined by a scanning electron microscope. Both of these techniques confirmed that copper had been etched right down to the tantalum underlayment.
P',~
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the deposition of copper films onto conducting metallic or metallic-like surfaces.
BACKGROUND OF THE INVENTION
In the electronics industry there is a steady trend towards manufacturing microprocessors of increasingly high speed and large information storage capacity.
This requires the individual electrical devices such as transi~ols, etc. within the microprocessors to be fabricated at an increasingly small scale. The metallic electrical interconnects between the devices also need to be miniaturized. As device and interconnect dimensions approach one-half to one-quarter of a micron, the choice of interconnect metal becomes critical. The large current densities resulting from small interconnect cross sectional areas can lead to major problems such as electromigration, stress migration, and voiding where the metal lines become fractured or otherwise physically degraded under operating conditions, a major drawback with aluminum alloys. Metal interconnects also need to provide the lowest electrical resistance path possible since resistance-capacitance delays become a dominant factor in circuitperformance at sub half micron levels. The alulllhlulll that is widely used in present day interconnect manufacturing is reasonably conductive (2.7 microohm cm), but needs to be alloyed with 0.5 to 4.0 atomic % Cu to ~"ini~"i~e the electromigration tendencies of the pure metal. Tungsten, also widely used, is electromigration resistant but is of higher resistivity (5.4 microohm cm). Considering these facts, copper should be an excellent interconnect metal as it is both highly conductive (1.7 microohm cm) and electromigration resistant.
k~
~,' 20s8~g3 Metall;c interconnects are typically horizontal lines (runners) or plugs (vias) that wire together devices in microprocessors. At feature sizes of >1 micron these metallic components can be built into the microcircuits by PVD (Physical Vapor Deposition) techniques such as sputtering or evaporation. In essence PVD consists of condensing a metal vapor onto a surface or into a hole or channel of a circuit where an electrical connection needs to be formed. Since this is a non-selective metallization, either a postdeposition clean-up (i.e. etch-back) or a predeposition masking of the substrate (i.e. the lift-off technique) is required in order to prepare individual discreet metal components. However, the severe surface topographies presented by sub-micron features preclude the effective use of PVD since this "line of sight" technique cannot provide a uniform conformal coating on such high aspect ratio highly convoluted surfaces. Specific examples of these shortcomings include the phenomena of geometrical shadowing and poor step coverage.
A superior process for producing these microscopic metal features is CVD
(Chemical Vapor Deposition). In this technique a volatile metal-organic compound in the gas phase is contacted with areas of a circuit where growth of a metal film (i.e. interconnect) is required. A surface catalyzed chemical reaction then occurs which leads to deposition of the desired metal. Since this is a chemical reaction, there is potential for it to provide surface selective metallization. That is, CVD metal deposition can be made to occur at only specific locations compared to the non-selective PVD processes. Also, since the metal film steadily grows on the desired surface it is of a uniform thickness and highly conformal even to severe geometries. In this respect CVD
is naturally suited to fabricating submicron high aspect ratio features.
An example of selective CVD metallization that is currently commercially practiced is the deposition of tungsten onto a silicon surface using tungsten hexaf1uoride as the volatile organometallic precursor(see T. Ohba, et al., "Tungsten and Other Advanced Metals for VLSI/ULSI Applications V," Ed. by S.
S. Wong and S. Furukawa, MRS, Pittsburgh, Pennsylvania, 273 (1990) ). The chemistry that drives this process can be divided into two steps. Initially the WF6 reacts with the elemental silicon surface to yield tungsten metal and volatile silicon hexafluoride. Hydrogen gas is then added to the system which 2(~8483 reduces further WF6 at the freshly formed metal surface thereby yielding additional tungsten and HF gas. Although this system currently enjoys widespread use as the only "selective" CVD metallization process that is widely commercially available, loss of selectivity can be observed and is commonly ascribed to the corrosive nature of HF. T. Ohba, et al., Tech. Dig.
IEDM, 213 (1987) teach the use of silane as a reducing agent for WF6 to achieve higher deposition rates while avoiding the production of HF gas.
Desirable selectivities for a copper CVD process include deposition onto conducting metallic or metallic like surfaces such as tungsten, tantalum or titanium nitride versus insulating surfaces such as silicon oxide. These metallic surfaces provide a diffusion barrier between the CVD copper and the underlying silicon substrate that the device is grown upon.
Copper films have previously been prepared via CVD using various copper precursors. Most of these compounds will only deposit copper metal at temperatures higher than 200~C with no significant selectivity between substrates such as diffusion barrier surfaces vs. silicon oxide. The best known and most frequently used CVD copper precursor is copper+2 bis(hexafluoroacetylacetonate). This highly fluorinated organometallic precursor is significantly more volatile than its parent unfluorinated complex copper+2 bis(acetylacetonate) and its ease of vaporization readily lends this compound towards CVD processes. The use of this compound as a general precursor for CVD copper metallization was first described by R. L. Van Hemert et al. J. Electrochem. Soc. (112), 1123 (1965) and by R. W. Moshier et al.
U. S. Patent 3,356,527. More recently Reisman, et al., J. Electrochemical Soc., Vol. 136, No. 11, November 1989 and A. E. Kaloyeros et al., Journal of Electronic Materials, Vol. 19, No. 3, 271 (1990) in two independent studies have also evaluated the use of this compound as a copper precursor for electronics applications. In these studies copper films were formed by contacting vapors of copper~2(hfac)2, mixed with either an inert gas (argon) or with hydrogen and contacting the mixture with a heated substrate surface.
In the case of using hydrogen the copper+2 atom in the precursor complex is formally reduced to copper metal while the hfac~l ligand becomes protonated to yield a neutral volatile compound. In the case of using an inert gas the copper+2(hfac)2 is simply pyrolyzed to give copper metal and fragments of the hfac ligand.
Pure copper is reported for the hydrogen reduction but oxygen and carbon are found in the films obtained by pyrolysis. However, the lowest deposition temperatures for either process is 250~C and no strong selectivities towards metallic vs. silicon oxide surfaces are reported. Copper films have also been prepared from copper+2(hfac)2 by plasma enhanced deposition, C. Oehr, H. Suhr, Appl. Phy. A. (45) 151-154 (1988),laser photothermal decomposition, F.A. Houle; C.R. Jones; T. Baum; C. Pico; C.A.Korae; Appl. Phys. Lett. (46) 204-206 (1985), and photochemical decomposition ofcopper+2(hfac)2 ethanol adducts, F.A. Houle; R.J. Wilson; T.H. Baum; J. Vac. Sci.
Technol. A (4), 2452-2458 (1986). Some of these methods yield fluorine cont~min~te~l films and none are reported to yield selective depositions. Similar hydrogen reduction of volatile copper compounds has also been demonstrated by Charles et al., U.S.
Patent 3,594,216 using copper+2 ~-ketoimine complexes at 400~C to deposit coppermetal films onto glass or quartz substrates. No mention of selectivity is made. G.S.
Girolami, et al., Chem. Mater. (1) 8-10 (1989) reported using copper+l t-butoxide to yield copper films CVD at 400~C, but the resultant films were hllpule in that they contained 5 atomic % oxygen.
The only CVD precursors known to deposit pure copper metal films below 200~C are the copper+l cyclopentadienyl phosphine compounds described by Beech et al., Chem. Mater. (2) 216-219 (1990), but these are also not reported to be strongly selective towards metallic or metallic like surfaces vs. silicon oxide or similar insulating dielectrics. An additional problem that this particular class of compounds faces for electronics applications is their potential to cont~min~te microcircuits with phosphorus, an element that is extensively used as a silicon dopant.
SUMMARY OF THE INVENTION
The present invention is an improved chemical vapor deposition process for selectively depositing pure, thin copper films on metallic or other electricallyconducting portions of a substrate surface. The improvement comprises contacting the substrate with a volatile organometallic copper complex having a vapor pressure greater than or equal to 0.01mm Hg at 100~C represented by the structural formula:
B
~n58483 O R2 () Cu+~ (Rl C-C-Il -R3) .L
where Rl and R3 are each independently C,-C8 perfluoroalkyl, R2 is H or Cl-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation.
This process provides for the selective deposition of pure copper films onto themetallic or other electrically conducting portions of a substrate surface at lowdeposition temperatures; i.e. from about 110~ to 190~C.
Additionally, it has been found that the deposition reaction can be reversed to cleanly and selectively etch deposited copper from a substrate surface. In this process, a substrate on which has been deposited a copper film is contacted with an organometallic copper complex and an olefin, CO or isonitrile, in the gas phase,represented by the structural formulae:
O R2 o CU+2 (Rl _ C -C -C -R3)2 + L2 where R', R2 and R3 are the same as above and L2 is the same as L defined above.
BRIEF DESCRIPTION OF THE DRAWINGS
The single Figure is a diagram of a conventional CVD apparatus used to carry out the process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
An improved chemical vapor deposition process has been developed for selectively depositing pure, thin copper films on metallic or other electricallyconducting portions of a substrate surface. The improvement comprises contacting the substrate with a volatile organometallic copper complex having a vapor pressure greater than or equal to 0.01mm Hg at 100~C. The copper complexes which are suitable for this deposition application can be represented by the structural formula:
C
i 2~5~83 O R2 o Cu+l (Rl _ C -C e -R3) ~L
where Rl and R3 are each independently Cl-C8 perfluoroalkyl, R2 is H or Cl-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation. In instances wherein L is an unsaturated hydrocarbon ligand, suitable examples include: ethylene, acetylene, l-octene, isobutylene, 1,5-cyclooctadiene, stilbene, diphenylacetylene, styrene, cyclooctene, 1,5,9-cyclododecatriene, 1,3-hexadiene, isopropylacetylene, l-decene, 2,5-bicycloheptadiene, l-octadecene, cyclopentene, octalin, methylene cyclohexane, diphenyl fulvene, l-octadecyne, benzyl cinnamate, benzal acetophenone, acrylonitrile, maleic anhydride, oleic acid, linolenic acid, acrylic acid, methyl methacrylate and diethyl maleate. Suitable isonitriles include methyl isocyanide, butyl ;socyanide, cyclohexyl isocyanide, phenylethyl isocyanide and phenyl isocyanide.
These compounds were originally disclosed in U. S. Patent 4,425,281 for use as complexing agents in a system of processes that separate carbon monoxide, alkenes or alkynes from various gas mixtures. Unexpectedly, we have found these compounds to be volatile compounds which, in their vapor form, can be used under certain conditions to selectively deposit copper metal films of high purity onto either metallic or other electrically conducting surfaces to the exclusion of deposition onto silicon oxide or other similar non-conducting (ie. insulating) surfaces. Such metallic or other electrically conducting surfaces include: W, TiN, Ta, Al, and the like. The deposition conditions are those typically employed in conventional copper CVD applications, with the exception that the present process allows for substantially lower deposition temperatures to be used, i.e., temperatures from about 110~ to 190~C, and preferably from 130~ to 180~C. While not intending to be bound by theory, the metallization process of the present invention is believed to occur via the following sequence of events:
a). Adsorbtion of the copper+l-olefin complex onto the surface(s) to be metallized 2 0 5 z~
b). surface catalyzed loss of olefin to yield an unstable copper+
species c). disproportionation of the unstable copper+l species to yield copper metal and a volatile copper+2 species.
This reaction mechanism is represented below for the complex copper+l(hfac)-COD where (s) indicates adsorbtion onto the surface and (g) indicates the compound in the gas phase (hfac being an abbreviation for the hexafluoroacetylacetonate anion and COD being an abbreviation for 1,5-cyclooctadiene). Both the COD and the Cu+2(hfac)2 are volatile byproducts.
1. 2Cu+l(hfac).COD(g) -----> 2Cu+l(hfac).COD(s) 2. 2Cu+l(hfac).COD(s) -----> 2Cu+l(hfac)(s) + 2COD(g) 3. 2Cu+l(hfac)(s) -----> Cu~(s) + Cu+2(hfac)2(g) The above described mechanism is unique in the field of CVD copper metallizat;on and offers a number of processing advantages. Stabilization of the +l oxidation state of copper is provided by coordination of an olefin and decomposition to copper metal is caused by loss of an olefin. Therefore, it is possible to control the copper deposition temperature, the rate of deposition and the resulting film morphology by increasing the concentration (i.e. pressure) of the olefin in the system or by adding different olefins.
Similarly, normally unstable volatile olefin complexes can be prepared by either using high pressures of olefin to stabilize copper+l and then effecting a CVD deposition by releasing the pressure or, using low temperatures and high olefin pressures to stabilize copper+l then effecting a copper deposition by warming and/or pressure drop.
The present process has the ability to selectively deposit copper films having small grain size at low temperatures, i.e., from 110~to 190~C, without significantly compromising the growth rate of the film. The small grain size of the deposited metal minimizes the need for post deposition planarization.
Additionally, the ability to deposit copper at these lower temperatures is especially important for the so called upper-level metals in multi-metal layer 20~483 ICs as excessive heat is to be avoided during the later stages of microprocessor fabrication to prevent thermally induced interdiffusion of of layer materials and dopants at device interfaces. Also, since useful deposition rates, appropriate grain size etc. can be accomplished below 200~C, standard photoresist materials can be used for patterning purposes via photolithographic techniques.
Additionally, the present process is advantageous in that it does not result in the release of corrosive or otherwise detrimental byproducts that can lead to a loss of selectivity or damage to the microprocessor substrate.
In an additional embodiment, hydrogen can be used in the CVD reduction of the organometallic copper complexes of the present invention, such as Cu+l(hfac)-olefin complexes, to yield metallic copper in a similar manner that it is reported to reduce Cu+2(hfac)2. This more effectively utilizes the precursor from the perspective that each metal center would yield metallic copper in contrast to the disproportionation reaction where only l/2 of the initial Cu+l centers yield copper metal. In instances in which this results in the loss of selectivity, an initial selective deposition in the absence of hydrogen can be utilized to deposit a seed layer of copper which would then be grown by subsequent CVD processing by hydrogen reduction. Optionally, other 20 reducing gases could also be used.
It has also been found that the present CVD reaction could be reversed such that copper metal deposited via a blanket deposition reaction could be removed, i.e., etched from the metallic surface area of a substrate. In accordance with this technique, a copper (+2) complex along with a suitable 25 olefin, both in the vapor phase, are brought into contact with a substrate onto which excess copper has been deposited. The copper metal on the surface of the substrate is converted into a volatile copper (+l) complex and is evaporated away from the metal. The general chemical equation for this etching reaction is as follows:
Cu~ + Cu+2(ligand)2 + 2 olefin > 2Cu+l(ligand)olefin Prior to the present invention, known etching processes were inappropriate for copper since prior processes resulted in the generation of copper halides 35 which are involatile and were left behind as surface contaminants.
2~5~83 g ExDerimental Synthesis:
In the following examples, temperatures are set forth uncorrected in degrees celcius. Unless otherwise noted, all parts and percentages are by weight. 1,1,1,5,5,5-hexafluoro-2,4-pentanedione was purchased from Fairfield Chemical Company (P.O. Box 20, Blythewood, SC 29106). 1,5-cyclooctadiene (i.e. COD), norbornadiene (i.e. NB), potassium hydride, copper+l oxide and copper+l chloride were purchased from Aldrich Chemical Co. (940 W. St. Paul Avenue, Milwaukee WI 53233). HPLC grade terahydrofuran (THF) and hexane were individually distilled from sodium benzophenone under an atmosphere of nitrogen prior to use. All operations in the preparation of metal complexes were carried out using standard Schlenk line techniques as described by D. F. Shriver in the "Manipulations of Air Sensitive Compounds" McGraw-Hill Publishing Co. Copper+l(hfac)-COD and [copper+l(hfac)]2-NB compounds, i.e. 1 and 2 respectively as shown in Table 1 were initially prepared by the method described by Doyle tOrganometallics, Vol. 4, No. 5, 830, (1985)]. This consisted of reacting cuprous oxide with one equivalent of hexafluoroacetylacetonate in THF solvent in the presence of one equivalent of olefin to yield the desired copper+l olefin complex and water, according to equation (1) shown below where the olefin is COD.
Cu20 + 2H-hfac + 2COD -----> 2Cu+l(hfac)-COD + H20 (1) However, we found that while this synthesis yielded the desired complex, it was heavily contaminated with Cu~2(hfac)2. Although Doyle claims that these complexes are moisture insensitive we have found during the course of our research that this is not so and that the presence of water leads to some of the copper+lolefin complex to decompose to copper+2 complex and copper, presumably via a disproportionation mechanism. This copper+2 contaminant then has to be removed via a series of recrystallizations and sublimations. To overcome this problem we developed a new "water free" synthesis where the potassium salt of hfac is reacted with cuprous chloride in THF solvent in the presence of one equivalent of olefin. This yields the desired copper olefin complex and potassium chloride by-product as shown below in equation 2:
2 0 ~ 3 K+ hfac~ + CuCl + olefin -----> Cu+l(hfac)-(olefin) + KCl (2) No Cu+2(hfac)2 was observed to form. ~e believe that this represents a generic route to any copper+l (~-diketonate).olefin complex. An example of 5 this route is shown below for the synthesis of copper+l(hfac)-COD:
Under a blanket of dry nitrogen 0.80g (2x10-2 moles) of potassium hydride are charged into a 100 ml Schlenk flask fitted with a rubber septum. 25 ml of dry tetrahydrofuran (THF) solvent are then added to the hydride via canula, the nitrogen atmosphere vented and 2.82 ml (4.16 g 2x10-2 moles) of hexafluoroacetylacetonate slowly added via syringe over a 10 minute period with stirring. A vigorous evolution of hydrogen is observed and stirring is continued until it ceases. A second nitrogen filled 100 ml Schlenk flask is charged with 1.98 g (2x10-2 moles) of cuprous chloride and 10 ml of dry THF
solvent are added into the flask along with the 2.54 ml (2x10-2 moles) of 15 1,5-cyclooctadiene. The initial potassium hexafluoroacetylacetonate solutionis then added via canula into the second flask with stirring. A bright yellow coloration is observed. After two hours of stirring at room temperature the solution is filtered under nitrogen to yield a clear yellow solution. The THF
is then evaporated to give an 80X yield of copper+l(hfac)-COD as a bright 20 yellow crystalline solid which can be further purified by recrystallization from dry hexane or sublimation at 65~C, 10-3 torr.
The selective metallizations of various substrates were performed using the apparatus shown in the accompanying figure. Under an atmosphere of nitrogen the source chamber 1 was loaded with 0.5-1.5 g of volatile copper+l hexafluoroacetylacetonate-olefin complex and then fitted to the precursor feed tube 3. Valve 5 was then closed. The susceptor 7 was then fitted with two silicon coupons 8 & 9, side by side, one bearing a silicon oxide surface and the other a metallized surface (i.e. TiN, Ta etc.). Alternatively, just one coupon bearing a silicon oxide/metal patterned surface (e.g. a W/SiO2 FLTC) was fitted to the susceptor. The entire susceptor assembly was then loaded into the deposition chamber 11 and a teflon stopper 12 was fitted in the top of the deposition chamber 11 through which a thermocouple 14 passes from the -~ 20384~3 susceptor 7 to a temperature controller, and a heater rod 16 passes from the temperature controller to the suscepter 7. A condensor 13 was then connected to deposition chamber 11 with valve 15 closed. A vacuum line 17 and two cold water lines 19 & 21 were then connected to condensor 13. Valves 5 and 15 were 5 then opened and the entire apparatus evacuated to 50 mtorr pressure. After a few minutes valve 5 is closed and the entire apparatus was lowered into a thermostated oil bath set at the desired source temperature up to the immersion line indicated. The thermostated heat for the susceptor was turned on and the susceptor allowed to reach the predetermined temperature (from 130-180~C). The apparatus was then left one hour or longer under vacuum (50 mtorr). The cooling water to the condensor was then turned on. After this time period valve 5 was opened thereby allowing vapors of the precursor to be drawn through the deposition chamber and to deposit a copper film on the susceptor and its mounted substrate(s). At the end of a run valve 5 was shut, the entire apparatus was backfilled with nitrogen gas and the susceptor assembly removed. Cu+2(hfac)2 was observed as sublimate collected onto the cold finger of the condensor along with unreacted Cu~hfac.olefin complex.
In Example 10 a similar piece of equipment was utilized to show that compound 1 could be vaporized at 105~C in a flow of dry nitrogen at one 20 atmosphere pressure and the resultant vapor passed over a silicon coupon at 150~C to yield a film of pure copper metal.
The results of these metallizations along with the specific complexes, substrates, and reaction conditions are listed in Table 1 below. Selectivity was determined by both visual inspection of the coupons at 200-lOOOX using an 25 optical microscope and by a scanning electron microscope (SEM) to determine the presence or absence of copper. The thickness of each deposited film was determined by viewing them edge on in SEM. The purity of the copper deposited was determined via Auger electron spectroscopy depth profiling. The purity of the copper films deposited onto TiN and Ta surfaces were measured from the metallized coupons used in runs 8 & 9 respectively. The purity of the copper film deposited onto tungsten was measured from the FLTC wafer used in run 2.
In all cases the purity of the copper was found to be >99.9Z with carbon, oxygen, and fluoride being below detectable limits.
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CY _ N ~ ~ Ir~ C1~r-- r-- --N t~) ~ N
A run was carried out to demonstrate the ability to etch excess copper from the surface of a substrate. This process was demonstrated using Cu+2(hfac)2 along with l-tridecene as the olefin slnce the volatl1ities of both are comparable. 1.09 of Cu+2(hfac)2 was added to 3 ml of l-tridecene and the mixture heated to 60~C then cooled to room temperature. Some copper complex precipitated out and was discarded. The saturated solutlon of complex in l-tridecene was then heated to 120~C and 200 ml/min of nitrogen bubbled lo through it to produce a nitrogen/complex/olefin vapor mixture. This vapor was then passed over a copper covered surface heated to 120~C for one hour, resulting in an etching of the copper surface. The etched sample was a silicon coupon that had been covered sequentially with 5000~ of silicon oxide, 1200~ of tantalum and lOoOA of copper. The surface of the coupon was partially masked with polyimide tape such that only a narrow trench of copper was exposed to the etch vapors. Once the etch was completed, the tape was removed and the extent of the etch determined by measuring the depth of copper removed from the surface via a stylus profilometer. In this technique, a sapphire stylus point contacts and tracks across the surFace of the etched coupon and directly measures ;ts surface topography in units of Angstroms. In addition, the etched surface was also examined by a scanning electron microscope. Both of these techniques confirmed that copper had been etched right down to the tantalum underlayment.
P',~
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for the chemical vapor deposition of a copper metal film onto a substrate, wherein at least a portion of the surface of said substrate is metallic, by contacting said substrate with a volatile organometallic copper precursor in the gas phase, the improvement for selectively depositing said copper film on the metallic portion of the surface of the substrate, at a deposition temperature from 110 to 190°C
which comprises:
using as said volatile organometallic copper precursor a complex having a vapor pressure greater than or equal to 0.01mm Hg at 100°C represented bythe structural formula:
where R1 and R3 are each independently C1-C8 perfluoroalkyl, R2 is H or C1-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation.
which comprises:
using as said volatile organometallic copper precursor a complex having a vapor pressure greater than or equal to 0.01mm Hg at 100°C represented bythe structural formula:
where R1 and R3 are each independently C1-C8 perfluoroalkyl, R2 is H or C1-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon ligand containing at least one non-aromatic unsaturation.
2. The process of Claim 1 wherein R2 is H.
3. The process of Claim 1 wherein the volatile copper organic precursor is Cu+1(hexafluoroacetylacetonate-1)~ 1,5-cyclooctadiene.
4. The process of Claim 1 wherein the volatile copper organic precursor is [Cu+1(hexafluoroacetylacetonate-1)]2~ norbornadiene.
5. The process of Claim 1 wherein the deposition temperature is from 130 to 180°C.
6. The process of Claim 1 wherein the surface onto which the copper metal film is deposited is selected from the group consisting of: W, TiN, Ta, and Al.
7. The process of Claim 1 wherein said substrate is contacted with hydrogen gas along with the organometallic precursor.
8. A process for selectively etching a copper film from the surface of a substrate, said process comprising:
contacting the substrate having a copper film surface with an organometallic copper complex and a ligand, both in the gas phase and at a temperature from 110° to 190°C, wherein said complex and saidligand are represented by the structural formulae:
where R1 and R3 are each independently C1-C8 perfluoroalkyl, R2 is H or C1-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon containing at least one non-aromatic unsaturation.
contacting the substrate having a copper film surface with an organometallic copper complex and a ligand, both in the gas phase and at a temperature from 110° to 190°C, wherein said complex and saidligand are represented by the structural formulae:
where R1 and R3 are each independently C1-C8 perfluoroalkyl, R2 is H or C1-C8 perfluoroalkyl and L is carbon monoxide, an isonitrile, or an unsaturated hydrocarbon containing at least one non-aromatic unsaturation.
9. The process of Claim 8 wherein R2 is H.
10. The process of Claim 8 wherein L is an olefin.
11. The process of Claim 10 wherein the organometallic copper complex is Cu+2(hexafluoroacetylacetonate-1)2 and the olefin is l-tridecene.
12. The process of Claim 8 wherein said substrate is contacted with the organometallic copper complex at a temperature from 130° to 180°C.
13. A process for the synthesis of a Cu+1(.beta.-diketonate)~olefin complex said process comprising: reacting the corresponding potassium salt of the (.beta.-diketonate) with cuprous chloride in a suitable solvent in the presence of one equivalent of the corresponding olefin.
14. The process in accordance with Claim 13 wherein said solvent is tetrahydrofuran.
15. The process in accordance with Claim 14 wherein said (.beta.-diketonate) is hexafluoroacetylacetonate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/636316 | 1990-12-31 | ||
| US07/636,316 US5098516A (en) | 1990-12-31 | 1990-12-31 | Processes for the chemical vapor deposition of copper and etching of copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2058483A1 CA2058483A1 (en) | 1992-07-01 |
| CA2058483C true CA2058483C (en) | 1999-01-05 |
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ID=24551364
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058483A Expired - Fee Related CA2058483C (en) | 1990-12-31 | 1991-12-27 | Process for the chemical vapor deposition of copper |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5098516A (en) |
| EP (1) | EP0493754B1 (en) |
| JP (2) | JPH0649942B2 (en) |
| KR (1) | KR940005327B1 (en) |
| CA (1) | CA2058483C (en) |
| DE (1) | DE69111587T2 (en) |
| IE (1) | IE73257B1 (en) |
Families Citing this family (84)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316796A (en) * | 1990-03-09 | 1994-05-31 | Nippon Telegraph And Telephone Corporation | Process for growing a thin metallic film |
| US5273775A (en) * | 1990-09-12 | 1993-12-28 | Air Products And Chemicals, Inc. | Process for selectively depositing copper aluminum alloy onto a substrate |
| AU4398093A (en) * | 1992-06-01 | 1993-12-30 | Martin Marietta Energy Systems, Inc. | Ultralight electromagnetic interference shielding and method for making same |
| US5264248A (en) * | 1992-08-03 | 1993-11-23 | General Electric Company | Adhesion of metal coatings of polypyromellitimides |
| US5387315A (en) * | 1992-10-27 | 1995-02-07 | Micron Technology, Inc. | Process for deposition and etching of copper in multi-layer structures |
| US5358743A (en) * | 1992-11-24 | 1994-10-25 | University Of New Mexico | Selective and blanket chemical vapor deposition of Cu from (β-diketonate)Cu(L)n by silica surface modification |
| US5368687A (en) * | 1993-03-15 | 1994-11-29 | Micron Technology, Inc. | Semiconductor processing method of etching insulating inorganic metal oxide materials and method of cleaning metals from the surface of semiconductor wafers |
| US5322712A (en) * | 1993-05-18 | 1994-06-21 | Air Products And Chemicals, Inc. | Process for improved quality of CVD copper films |
| US5431774A (en) * | 1993-11-30 | 1995-07-11 | Texas Instruments Incorporated | Copper etching |
| KR0147682B1 (en) * | 1994-05-24 | 1998-11-02 | 구본준 | Method for manufacturing metal wiring of semiconductor device |
| US5412129A (en) * | 1994-06-17 | 1995-05-02 | Dicarolis; Stephen A. | Stabilization of precursors for thin film deposition |
| US5464666A (en) * | 1995-02-06 | 1995-11-07 | Air Products And Chemicals, Inc. | Process for chemical vapor codeposition of copper and aluminum alloys |
| JP2622671B2 (en) * | 1995-03-07 | 1997-06-18 | 株式会社トリケミカル研究所 | Method for producing copper β-diketonate complex |
| US5814238A (en) * | 1995-10-12 | 1998-09-29 | Sandia Corporation | Method for dry etching of transition metals |
| KR0179797B1 (en) * | 1995-12-29 | 1999-04-15 | 문정환 | Method of forming cu thin film with bias voltage supplied |
| DE19637194C2 (en) * | 1996-09-12 | 2003-10-02 | Mattson Thermal Products Gmbh | Gas mixture and method for dry etching metals, especially copper, at low temperatures |
| US6090960A (en) * | 1997-01-07 | 2000-07-18 | Sharp Laboratories Of America, Inc. | Precursor with (methoxy) (methyl) silylolefin ligand to deposit copper and method same |
| US5767301A (en) * | 1997-01-21 | 1998-06-16 | Sharp Microelectronics Technology, Inc. | Precursor with (alkyloxy)(alkyl)-silylolefin ligand to deposit copper |
| FR2760743B1 (en) | 1997-03-13 | 1999-07-23 | Centre Nat Rech Scient | NOVEL COPPER PRECURSORS (I) FOR CHEMICAL GAS DEPOSITION OF METAL COPPER |
| US5939334A (en) * | 1997-05-22 | 1999-08-17 | Sharp Laboratories Of America, Inc. | System and method of selectively cleaning copper substrate surfaces, in-situ, to remove copper oxides |
| KR100256669B1 (en) * | 1997-12-23 | 2000-05-15 | 정선종 | Chemical vapor deposition apparatus and method for forming copper film using the same |
| KR100296959B1 (en) * | 1998-01-19 | 2001-09-22 | 정명식 | Organo cuprous complex precursor useful for chemical vapor deposition of copper |
| KR100259357B1 (en) * | 1998-02-07 | 2000-06-15 | 김영환 | Wiring fabrication method for semiconductor device |
| JP3334605B2 (en) * | 1998-05-07 | 2002-10-15 | 三菱電機株式会社 | Electrode-forming CVD raw material, and capacitor electrode and wiring film formed using the same |
| US6461675B2 (en) * | 1998-07-10 | 2002-10-08 | Cvc Products, Inc. | Method for forming a copper film on a substrate |
| US6102993A (en) * | 1998-08-03 | 2000-08-15 | Advanced Technology Materials, Inc. | Copper precursor composition and process for manufacture of microelectronic device structures |
| KR20000013302A (en) * | 1998-08-06 | 2000-03-06 | 최형수 | Glass copper precursor for chemical vapor deposition |
| US6190732B1 (en) | 1998-09-03 | 2001-02-20 | Cvc Products, Inc. | Method and system for dispensing process gas for fabricating a device on a substrate |
| US6037001A (en) * | 1998-09-18 | 2000-03-14 | Gelest, Inc. | Method for the chemical vapor deposition of copper-based films |
| US6066196A (en) * | 1998-09-18 | 2000-05-23 | Gelest, Inc. | Method for the chemical vapor deposition of copper-based films and copper source precursors for the same |
| US6245261B1 (en) * | 1998-12-11 | 2001-06-12 | Sharp Laboratories Of America, Inc. | Substituted phenylethylene precursor and synthesis method |
| US6204176B1 (en) * | 1998-11-10 | 2001-03-20 | Sharp Laboratories Of America, Inc. | Substituted phenylethylene precursor deposition method |
| US7012292B1 (en) * | 1998-11-25 | 2006-03-14 | Advanced Technology Materials, Inc | Oxidative top electrode deposition process, and microelectronic device structure |
| US6046364A (en) * | 1998-12-07 | 2000-04-04 | Air Products And Chemicals, Inc. | Regeneration of metal CVD precursors |
| US6294836B1 (en) | 1998-12-22 | 2001-09-25 | Cvc Products Inc. | Semiconductor chip interconnect barrier material and fabrication method |
| AU2627100A (en) * | 1999-01-21 | 2000-08-07 | Midwest Research Institute | Passivating etchants for metallic particles |
| US6245655B1 (en) | 1999-04-01 | 2001-06-12 | Cvc Products, Inc. | Method for planarized deposition of a material |
| US6337148B1 (en) | 1999-05-25 | 2002-01-08 | Advanced Technology Materials, Inc. | Copper source reagent compositions, and method of making and using same for microelectronic device structures |
| US6110530A (en) * | 1999-06-25 | 2000-08-29 | Applied Materials, Inc. | CVD method of depositing copper films by using improved organocopper precursor blend |
| JP3925780B2 (en) * | 1999-12-15 | 2007-06-06 | エー・エス・エムジニテックコリア株式会社 | Method for forming copper wiring and thin film using catalyst and chemical vapor deposition |
| US6627995B2 (en) | 2000-03-03 | 2003-09-30 | Cvc Products, Inc. | Microelectronic interconnect material with adhesion promotion layer and fabrication method |
| US6589329B1 (en) | 2000-03-09 | 2003-07-08 | Advanced Technology Materials, Inc. | Composition and process for production of copper circuitry in microelectronic device structures |
| US6417369B1 (en) | 2000-03-13 | 2002-07-09 | Advanced Technology Materials, Inc. | Pyrazolate copper complexes, and MOCVD of copper using same |
| EP1264817A1 (en) | 2000-03-14 | 2002-12-11 | Nissan Chemical Industries, Ltd. | $g(b)-DIKETONATOCOPPER(I) COMPLEX CONTAINING ALLENE COMPOUND AS LIGAND AND PROCESS FOR PRODUCING THE SAME |
| US6444263B1 (en) | 2000-09-15 | 2002-09-03 | Cvc Products, Inc. | Method of chemical-vapor deposition of a material |
| KR100382533B1 (en) * | 2000-12-13 | 2003-05-09 | 삼성전자주식회사 | Ligand and organo-metal precursor using thereof |
| US7084080B2 (en) * | 2001-03-30 | 2006-08-01 | Advanced Technology Materials, Inc. | Silicon source reagent compositions, and method of making and using same for microelectronic device structure |
| US6509266B1 (en) | 2001-04-02 | 2003-01-21 | Air Products And Chemicals, Inc. | Halogen addition for improved adhesion of CVD copper to barrier |
| KR100600468B1 (en) * | 2001-04-16 | 2006-07-13 | 샤프 가부시키가이샤 | Process for producing cycloalkene copper precursors |
| US7049226B2 (en) * | 2001-09-26 | 2006-05-23 | Applied Materials, Inc. | Integration of ALD tantalum nitride for copper metallization |
| US6534666B1 (en) | 2001-12-27 | 2003-03-18 | Air Products And Chemicals, Inc. | Use of water and acidic water to purify liquid MOCVD precursors |
| US6911391B2 (en) * | 2002-01-26 | 2005-06-28 | Applied Materials, Inc. | Integration of titanium and titanium nitride layers |
| FR2839982B1 (en) | 2002-05-22 | 2005-04-15 | Centre Nat Rech Scient | PRECURSOR COMPOSITION FOR COPPER DEPOSITION ON A SUPPORT |
| US20040009665A1 (en) * | 2002-06-04 | 2004-01-15 | Applied Materials, Inc. | Deposition of copper films |
| EP2182088B1 (en) * | 2002-11-15 | 2013-07-17 | President and Fellows of Harvard College | Atomic layer deposition using metal amidinates |
| US7217649B2 (en) * | 2003-03-14 | 2007-05-15 | Lam Research Corporation | System and method for stress free conductor removal |
| US7540935B2 (en) * | 2003-03-14 | 2009-06-02 | Lam Research Corporation | Plasma oxidation and removal of oxidized material |
| US7232766B2 (en) * | 2003-03-14 | 2007-06-19 | Lam Research Corporation | System and method for surface reduction, passivation, corrosion prevention and activation of copper surface |
| US7140374B2 (en) * | 2003-03-14 | 2006-11-28 | Lam Research Corporation | System, method and apparatus for self-cleaning dry etch |
| US7009281B2 (en) * | 2003-03-14 | 2006-03-07 | Lam Corporation | Small volume process chamber with hot inner surfaces |
| US6939796B2 (en) * | 2003-03-14 | 2005-09-06 | Lam Research Corporation | System, method and apparatus for improved global dual-damascene planarization |
| US6821899B2 (en) * | 2003-03-14 | 2004-11-23 | Lam Research Corporation | System, method and apparatus for improved local dual-damascene planarization |
| US7129167B1 (en) | 2003-03-14 | 2006-10-31 | Lam Research Corporation | Methods and systems for a stress-free cleaning a surface of a substrate |
| US7078344B2 (en) * | 2003-03-14 | 2006-07-18 | Lam Research Corporation | Stress free etch processing in combination with a dynamic liquid meniscus |
| DE10319454A1 (en) * | 2003-04-29 | 2004-11-18 | Merck Patent Gmbh | Dikupfer (I) oxalate complexes as a precursor for metallic copper deposition |
| US7311946B2 (en) * | 2003-05-02 | 2007-12-25 | Air Products And Chemicals, Inc. | Methods for depositing metal films on diffusion barrier layers by CVD or ALD processes |
| US9029189B2 (en) * | 2003-11-14 | 2015-05-12 | President And Fellows Of Harvard College | Bicyclic guanidines, metal complexes thereof and their use in vapor deposition |
| US6838573B1 (en) | 2004-01-30 | 2005-01-04 | Air Products And Chemicals, Inc. | Copper CVD precursors with enhanced adhesion properties |
| US7166732B2 (en) * | 2004-06-16 | 2007-01-23 | Advanced Technology Materials, Inc. | Copper (I) compounds useful as deposition precursors of copper thin films |
| US20060102895A1 (en) * | 2004-11-16 | 2006-05-18 | Hendrix Bryan C | Precursor compositions for forming tantalum-containing films, and tantalum-containing barrier films and copper-metallized semiconductor device structures |
| US7205422B2 (en) * | 2004-12-30 | 2007-04-17 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate and metal β-diiminate complexes |
| US7034169B1 (en) | 2004-12-30 | 2006-04-25 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate complexes |
| US9312557B2 (en) * | 2005-05-11 | 2016-04-12 | Schlumberger Technology Corporation | Fuel cell apparatus and method for downhole power systems |
| US7713907B2 (en) * | 2006-03-06 | 2010-05-11 | Uchicago Argonne, Llc | Method of preparing size-selected metal clusters |
| US20080206445A1 (en) * | 2007-02-22 | 2008-08-28 | John Peck | Selective separation processes |
| KR100683030B1 (en) * | 2006-11-23 | 2007-02-16 | 주식회사 이정이앤씨 | Waterproof electric flexible tube for building |
| WO2008069821A1 (en) * | 2006-12-05 | 2008-06-12 | Advanced Technology Materials, Inc. | Metal aminotroponiminates, bis-oxazolinates and guanidinates |
| US7750173B2 (en) * | 2007-01-18 | 2010-07-06 | Advanced Technology Materials, Inc. | Tantalum amido-complexes with chelate ligands useful for CVD and ALD of TaN and Ta205 thin films |
| JP5461390B2 (en) * | 2007-05-21 | 2014-04-02 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | New metal precursors for semiconductor applications |
| TWI426154B (en) * | 2007-05-21 | 2014-02-11 | Air Liquide | New cobalt precursors for semiconductor applications |
| US8758867B2 (en) * | 2007-09-17 | 2014-06-24 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés George Claude | Neutral ligand containing precursors and methods for deposition of a metal containing film |
| US8263795B2 (en) * | 2007-11-05 | 2012-09-11 | Air Products And Chemicals, Inc. | Copper precursors for thin film deposition |
| US20090130466A1 (en) * | 2007-11-16 | 2009-05-21 | Air Products And Chemicals, Inc. | Deposition Of Metal Films On Diffusion Layers By Atomic Layer Deposition And Organometallic Precursor Complexes Therefor |
| US9705124B2 (en) * | 2012-02-27 | 2017-07-11 | The Johns Hopkins University | High energy density Li-ion battery electrode materials and cells |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3356527A (en) * | 1964-04-23 | 1967-12-05 | Ross W Moshier | Vapor-plating metals from fluorocarbon keto metal compounds |
| US3594216A (en) * | 1969-06-19 | 1971-07-20 | Westinghouse Electric Corp | Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate |
| IT1083401B (en) * | 1977-05-27 | 1985-05-21 | Alfachimici Spa | ACID SOLUTION FOR SELECTIVE COPPER ATTACK |
| US4321073A (en) * | 1980-10-15 | 1982-03-23 | Hughes Aircraft Company | Method and apparatus for forming metal coating on glass fiber |
| CA1178290A (en) * | 1981-07-13 | 1984-11-20 | Gerald Doyle | Copper or silver complexes with fluorinated diketonates and unsaturated hydrocarbons |
| US4425281A (en) * | 1981-07-13 | 1984-01-10 | Exxon Research And Engineering Co. | Copper or silver complexes with fluorinated diketones and unsaturated ligands |
| US4622095A (en) * | 1985-10-18 | 1986-11-11 | Ibm Corporation | Laser stimulated halogen gas etching of metal substrates |
| US4948623A (en) * | 1987-06-30 | 1990-08-14 | International Business Machines Corporation | Method of chemical vapor deposition of copper, silver, and gold using a cyclopentadienyl/metal complex |
| JP2811004B2 (en) * | 1988-05-23 | 1998-10-15 | 日本電信電話株式会社 | Metal thin film growth method and apparatus |
| US4904340A (en) * | 1988-10-31 | 1990-02-27 | Microelectronics And Computer Technology Corporation | Laser-assisted liquid-phase etching of copper conductors |
-
1990
- 1990-12-31 US US07/636,316 patent/US5098516A/en not_active Expired - Lifetime
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1991
- 1991-12-20 DE DE69111587T patent/DE69111587T2/en not_active Expired - Fee Related
- 1991-12-20 EP EP91121887A patent/EP0493754B1/en not_active Expired - Lifetime
- 1991-12-25 JP JP3357099A patent/JPH0649942B2/en not_active Expired - Fee Related
- 1991-12-27 CA CA002058483A patent/CA2058483C/en not_active Expired - Fee Related
- 1991-12-30 IE IE456591A patent/IE73257B1/en not_active IP Right Cessation
- 1991-12-30 KR KR1019910025166A patent/KR940005327B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0493754B1 (en) | 1995-07-26 |
| US5098516A (en) | 1992-03-24 |
| DE69111587D1 (en) | 1995-08-31 |
| JPH10245678A (en) | 1998-09-14 |
| EP0493754A1 (en) | 1992-07-08 |
| JPH0649942B2 (en) | 1994-06-29 |
| CA2058483A1 (en) | 1992-07-01 |
| JPH04318170A (en) | 1992-11-09 |
| IE914565A1 (en) | 1992-07-01 |
| JP3262271B2 (en) | 2002-03-04 |
| KR920012515A (en) | 1992-07-27 |
| IE73257B1 (en) | 1997-05-21 |
| DE69111587T2 (en) | 1996-01-11 |
| KR940005327B1 (en) | 1994-06-16 |
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