US20050223978A1 - Technique for high efficiency metalorganic chemical vapor deposition - Google Patents
Technique for high efficiency metalorganic chemical vapor deposition Download PDFInfo
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- US20050223978A1 US20050223978A1 US11/146,953 US14695305A US2005223978A1 US 20050223978 A1 US20050223978 A1 US 20050223978A1 US 14695305 A US14695305 A US 14695305A US 2005223978 A1 US2005223978 A1 US 2005223978A1
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- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 108
- 239000000376 reactant Substances 0.000 claims abstract description 94
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims description 118
- 239000004065 semiconductor Substances 0.000 claims description 54
- 238000000151 deposition Methods 0.000 claims description 53
- 230000008021 deposition Effects 0.000 claims description 45
- 239000012159 carrier gas Substances 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000012705 liquid precursor Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- DODHYCGLWKOXCD-UHFFFAOYSA-N C[Pt](C1(C=CC=C1)C)(C)C Chemical compound C[Pt](C1(C=CC=C1)C)(C)C DODHYCGLWKOXCD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- -1 methyl compound Chemical group 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 abstract description 35
- 230000008569 process Effects 0.000 description 17
- 239000004020 conductor Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000002912 waste gas Substances 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
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- 239000000356 contaminant Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019017 PtRh Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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Images
Classifications
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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
- C23C16/44—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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
- H01L28/65—Electrodes comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
Definitions
- the present invention relates to semiconductor processing and, in particular, concerns a metalorganic chemical vapor deposition (MOCVD) technique for forming component layers, such as platinum layers, in a manner that results in more efficient deposition of the component layer onto the surface of a semiconductor device.
- MOCVD metalorganic chemical vapor deposition
- a typical device formed by semiconductor processing is a capacitor.
- a capacitor is formed in an opening in an isolation layer of a semiconductor device and has two electrodes that are positioned within the opening with a dielectric separating the electrodes so as to cover both the side walls and the bottom floor of the opening.
- the electrode formed so as to uniformly cover the side walls and bottom walls of the opening.
- Three dimensional capacitors are but one example of a device that is increasingly more difficult to fabricate due to decreasing device dimensions leading to difficulties with conformal covering of the device surface.
- Other devices in which this problem occurs include vias, electrodes and conductive lines.
- CVD Chemical Vapor Deposition
- platinum is viewed as an ideal electrode material for high-K capacitors in DRAM applications due to its relatively high work function.
- This high work function forms an increased energy barrier inhibiting leakage migration of charge carriers between electrodes through an intervening dielectric.
- platinum is also generally not oxidizable such that the electrode's resistivity is not increased as a result of exposure to oxygen containing compounds contained within the semiconductor environment.
- platinum is also strongly favored for formation of electrodes and 3-dimensional semiconductor structures, such as capacitors, conductors, vias and the like, due to its particularly advantageous step coverage when applied using chemical vapor deposition (CVD) techniques.
- CVD chemical vapor deposition
- platinum can be used to coat 3-dimensional structures through chemical vapor deposition such that the vertical side walls and the horizontal bottom surfaces are adequately covered by the deposited platinum.
- a platinum precursor and other reactants are introduced into the CVD chamber and the platinum carried by a precursor gas is then deposited onto the surface of the semiconductor substrate through thermal decomposition or reaction with another reactant gas, such as O 2 , N 2 O, or H 2 .
- the platinum is carried in the precursor gas, that often comprises an organic compound.
- the platinum atom is bonded to the organic compound to permit the platinum atoms to be transferred in the gas phase. This enables the Pt to be conformally deposited over the surface of the wafer as the organic compound facilitates improved step coverage.
- the platinum precursor gas used for deposition is particularly expensive, on the order of $100 per gram. It has been observed that typical CVD platinum deposition techniques result in enormous waste of this expensive platinum precursor gas as only a small proportion of the platinum carried by the precursor gas is actually being deposited on the semiconductor wafer positioned in the CVD chamber. Hence, not only are current CVD platinum deposition techniques slow, they are also particularly inefficient in delivering platinum to the wafer. This results in considerable waste of expensive material and increases the cost of manufacturing semiconductor devices that require 3-dimensional conductive structures, like electrodes or conductors.
- the deposition process also results in the possible deposition of hydrocarbon byproducts on the surface of the semiconductor device which can become incorporated into or adsorbed onto the surface of the deposited film contaminating the film and inhibiting further deposition.
- the deposition of platinum in one typical process proceeds by the formula: (C 5 H 5 )Pt(CH 3 ) 3 +H 2 ⁇ Pt(film)+CH 4 +other hydrocarbons
- the other hydrocarbons may not be volatile enough at the deposition temperature and thus stay on the surface of the film following deposition. This can result in contamination of the film and inhibit further deposition of the platinum film.
- the present invention comprises a method of forming a conductive layer comprising (a) positioning a semiconductor device within a CVD chamber, (b) exposing the semiconductor device to a precursor gas containing a conductive element and a reactant to form the conductive layer for a first period of time, (c) exposing the semiconductor substrate to a reactant so that the reactant reacts with organic compounds contained within the conductive layer, and (d) reintroducing the precursor gas into the CVD chamber following exposure of the semiconductor substrate to the reactant so as to further form the conductive layer on the semiconductor device.
- a semiconductor device with a defined opening for a 3-dimensional capacitor is positioned within a CVD chamber and is exposed to a precursor gas containing platinum which is then deposited using chemical vapor deposition techniques.
- a reactant is also introduced into the CVD chamber wherein the deposited platinum material is exposed to the reactant.
- the reactant can comprise any of a number of elements, compounds or processes, such as, for example, the introduction of a gas such as H 2 , N 2 O, NO, H 2 O, O 2 , ozone, or some other oxygen containing ambient, into the CVD chamber or with the enhancement of plasma or UV light.
- the conductor can comprise not only platinum, but also other conductive films such as Ir, Rh, Ni, Co, Cu, W, and the like.
- the reactant gas is introduced at the same time as the conductive precursor gas. In another embodiment, the reactant gas is introduced following the introduction of the precursor gas for a selected period of time. In either circumstance, the reactant gas reacts with the residual organic compounds so as to remove the residual organic compounds in or on the surface of the deposited films thereby increasing the deposition efficiency.
- Organic by-products can be adhered to the exposed surface of the deposited conductive layer.
- the organic compounds By introducing a reactant into the CVD chamber, the organic compounds can be removed by reaction with the reactants thereby making available more conductor nucleating sites and allowing greater absorption of the conductor precursor in the vapor phase.
- a system for forming a conductive layer on a semiconductor device includes a CVD chamber which receives the semiconductor device; a metal organic precursor gas source which provides a metal organic precursor gas with entrained conductive particles; a reactant source that provides a reactant to the CVD chamber and a controller which controls the delivery of conductive precursor gas and reactant into the CVD chamber.
- the controller allows for the delivery of the conductive precursor gas and the reactant into the chamber.
- the reactant is selected to react with organic compounds of the conductive precursor gas so as to remove the organic compound from the formed conductive layer.
- the system includes a sensor, such as, for example, a mass spectrometer, that provides a signal to the controller indicative of the deposition of the conductive precursor gas by the semiconductor device.
- a sensor such as, for example, a mass spectrometer
- the controller When the deposition drops below a particular threshold, such that there is increased waste of the conductive precursor gas, the controller then induces the delivery of the reactant into the chamber.
- FIG. 1 is a block diagram of one embodiment of a system for forming a conductive structure on a semiconductor device
- FIGS. 2A-2C are cross-sectional views of a semiconductor device illustrating one embodiment of a method by which a conductive structure is formed on the device;
- FIG. 3A is an illustration of a typical platinum precursor gas molecule used in a CVD process
- FIG. 3B is a chart illustrating the improved absorption characteristics of the process of the illustrated embodiments.
- FIG. 4 is a block diagram illustrating another embodiment of a system for forming a conductive structure on a semiconductor device.
- FIG. 5 is a flow chart illustrating one method of forming a conductive structure on a semiconductor device.
- FIG. I is a block diagram which illustrates one example of a system 100 for depositing a conductive layer on a semiconductor device in accordance with the illustrated embodiment.
- a CVD chamber 101 of a type known in the art is provided with a conductive precursor gas 105 that is used to deposit conductive layers and structures on semiconductor devices positioned within the CVD chamber 101 .
- a conductive carrier gas 103 containing conductive elements is provided by a conductive carrier gas source 102 and the conductive carrier gas 103 is supplied to a bubbler 104 that contains a liquid precursor.
- the conductive carrier gas 103 and the liquid precursor bind so as to allow the conductive element to be carried in a gas form in the conductive precursor gas 105 into the CVD chamber 101 so as to permit CVD coverage of the semiconductor devices in a manner known in the art.
- the conductive carrier gas 103 is a known platinum-based carrier gas, such as platinum entrained in N 2 O.
- the conductive carrier gas 103 is supplied to the bubbler 104 which, in this embodiment, contains a liquid methyl based precursor such that the conductive precursor gas 105 is comprised of (methylcyclopentadienyl) (trimethyl) platinum (MeCpPtMe 3 ).
- the use of the organic methyl compound in the conductive precursor gas 105 allows for better step coverage during CVD deposition than just supplying a platinum carrier gas directly into the CVD chamber 101 .
- the conductor precursor gas 105 is supplied to the CVD chamber 101 for a preselected period of time so as to allow the conductive element to coat the semiconductor device via chemical vapor deposition (CVD) techniques.
- CVD chemical vapor deposition
- the conductive precursor gas 105 is a Platinum conductive gas
- any of a number of different precursor gases used to form conductive films can be used without departing from the present invention. These gases include gases that entrain conductive elements such as Ir, Rh, Ni, Co, Cu, W, and the like.
- the system 100 includes a reactant source 106 that provides a reactant 107 into the CVD chamber 101 that is selected so as to interact with the organic compounds of the conductive precursor gas 105 to thereby facilitate more efficient deposition of the conductive elements contained within the conductive precursor gas 105 .
- the reactant source 106 provides the reactant 107 selected from the group comprising NH 3 , H 2 , N 2 , NO, N 2 O, O 2 , O 3 , or any other O containing ambient. Providing the reactant 107 into the CVD chamber 101 allows the conductive elements contained within the conductive precursor gas 105 to deposit on the surface of the semiconductor device.
- the illustrated system 100 also includes a waste gas receptacle 110 that receives waste gas 111 comprised of unused conductive precursor gas 105 and unused reactants 107 during the process.
- the reactant 107 and the conductive precursor gas 105 are simultaneously introduced into the CVD chamber 101 for a period of time that is selected to obtain a resulting conductive film of a desired thickness.
- the reactant 107 reacts with the contaminants contained within the film that may not otherwise be volatile enough at the deposition temperature and stay on the surface.
- the reactant 107 is an oxidizing agent, such as NO, N 2 O, O 2 , or O 3 , that reacts with the organic byproducts on the surface to give them sufficient energy to become a gas that can be removed as the waste gas 111 .
- the reactant 107 is a reducing agent such as NH 3 or H 2 .
- platinum is an active catalyst that absorbs hydrogen at its surface and it activates the molecules enough to react with carbon or methyl (CH 3 ) to form CH 4 and other hydrocarbons. The introduction of the reactant 107 helps to remove these other hydrocarbons.
- the reactant 107 and the conductive precursor gas 105 are introduced into the chamber 101 simultaneously until a film of a desired thickness is achieved. It will, however, be appreciated that the precursor gas 105 and the reactant gas 107 can be introduced sequentially until a film of a desired thickness is achieved without departing from the spirit of the present invention. It should be appreciated that introduced should be construed to mean both initiating the supply of an agent and also continuing to supply that agent for some period of time.
- FIGS. 2A-2C schematically illustrate the process of the illustrated embodiment in greater detail. More particularly, FIGS. 2A-2C provide a simplified illustration of how a conductive layer 160 , such as a lower electrode of a capacitor or a conductive, would be formed in an opening 156 that is adapted to receive, for example, a capacitor.
- a semiconductor device 150 which can comprise a semiconductor substrate 152 with an insulating layer 154 positioned thereon, is positioned within the CVD chamber 101 .
- the semiconductor device 150 includes the opening 156 formed in the insulating layer 154 which is then to be coated with the conductive layer 160 .
- the conductive precursor gas 105 is introduced into the CVD chamber 101 such that a conductive material, such as platinum, is deposited on the exposed surfaces of the semiconductor device 150 .
- a conductive material such as platinum
- the conductive precursor gas 105 illustrated in FIG. 4 results in a relatively high degree of step coverage of the conductive layer 160 on the horizontal surfaces and also on the vertical side wall surfaces of the semiconductor device 150 .
- the initial deposition of the conductive layer 160 results in organic compounds 162 occupying the surface nucleating sites of the conductive layer 160 .
- the organic compound 162 that comprises the methyl molecules poisons the exposed surface of the conductive layer 160 by covering the available platinum nucleating sites or by otherwise inhibiting further absorption of the conductive precursor gas 105 in the vapor phase.
- the reactant 107 is introduced into the CVD chamber 101 as the conductive precursor gas 105 .
- the reactant 107 preferably reacts with the organic compounds 162 thereby removing these compounds in the previously described manner to improve the deposition efficiency of the process.
- the process illustrated in FIG. 2A can thus be continued until a conductive layer 160 of a desired thickness is achieved.
- the simultaneous introduction of the conductive precursor gas 105 and the reactant 107 results in more efficient deposition as is illustrated in the chart of FIG. 3B discussed hereinbelow.
- the reactant 107 can also be introduced after the conductive precursor gas 105 has been introduced for a set period of time in the manner shown in FIG. 2B .
- the conductive precursor gas 105 can be initially introduced and the reactant 107 can then be introduced subsequently to remove the contaminants 162 and the conductive precursor gas 105 can then be reintroduced again.
- the flow of the conductive precursor gas 105 into the CVD chamber 101 is stopped and the semiconductor device 150 within the CVD chamber 101 is then exposed to a reactant 107 from the reactant source 106 .
- the reactant source 106 is selected to provide a reactant 107 that reacts with the organic compounds 162 of the conductive precursor gas 105 so as to remove at least some of the organic compounds 162 from conductive element nucleation sites within the conductive layer 160 .
- the reactant 107 as introduced subsequent to cessation of introduction of the conductive precursor gas 105 , comprises a reactant 107 selected from the group comprising N 2 O, O 2 , H 2 , NH 3 , NO, H 2 O, ozone, vacuum, and inert gas purge, such as with N 2 or argon.
- the reactant 107 also comprises providing supplemental plasma treatment and/or UV light to the CVD chamber 101 .
- the reactant 107 as introduced with the conductive precursor gas 105 comprises the same reactant 107 as introduced absent the introduction of the conductive precursor gas 105 .
- the reactant 107 as introduced absent the introduction of the conductive precursor gas 105 comprises alternative or additional components as the reactant 107 as introduced with the conductive precursor gas 105 .
- the reactant source 106 stops providing the reactant 107 into the CVD chamber 101 and the conductive precursor gas 105 is again provided into the CVD chamber 101 in the previously described manner.
- the reactant 107 has removed at least some of the organic compounds 162 from the conductive layer 160 that would otherwise inhibit further chemical vapor deposition of the conductive elements of the conductive precursor gas 105 , more conductive elements can be added to the conductive layer 160 by a subsequent chemical vapor deposition step.
- the process of forming the conductive layer 160 in this embodiment can either comprise introducing a conductive precursor gas 105 and a reactant 107 simultaneously into the CVD chamber 101 for a preselected period of time to form a conductive structure or sequentially introducing a conductive precursor gas 105 and a reactant 107 to form the conductive structure 160 .
- a conductive layer 160 is formed using an initial deposition step wherein a platinum precursor carrier gas is provided from the conductive carrier gas source 102 through the bubbler 104 at a rate of between 40 to 200 sccm with the platinum being encapsulated within a helium carrier.
- the bubbler 104 contains a liquid precursor at a temperature between 35° C. and 50° C., such that the resulting conductive precursor gas 105 emanating from the bubbler 104 has the chemical composition as illustrated in FIG. 3A .
- the resulting conductive precursor gas 105 is provided from the bubbler 104 to the CVD chamber 101 along with a simultaneous flow of N 2 O reactant 107 at a rate of 100 to 800 sccm from the reactant source 106 .
- This flow of conductive precursor gas 105 and reactant 107 is provided to the CVD chamber 101 for approximately 50 seconds to result in deposition of the conductive layer 160 .
- the flow of the conductive precursor gas 105 from the bubbler 104 is ceased while the flow of the N 2 O reactant 107 from the reactant source 106 is continued for 10 seconds.
- the N 2 O thus comprises the reactant 107 which reacts with the organic compounds 162 in the deposited layer 160 associated with the conductive precursor gas 105 so as to remove the organic compounds 162 from the deposited, conductive layer 160 in the manner described in conjunction with FIG. 2B .
- the conductive precursor gas 105 is provided for another 50 second interval and is then followed by a 10 second exposure of the conductive layer 160 to the N 2 O reactant 107 from the reactant source 106 . This process is repeated until a conductive layer 160 of a desired thickness is formed.
- resistivity of the deposited conductive layer 160 is inversely proportional to the thickness of the conductive layer 160 which indicates that there is a very significant increase in the deposition rate of the film using the process of the above-described embodiment.
- the Applicant has observed at least ten-fold increases in the deposition rate over known CVD deposition techniques for conductive layers of this type. Hence, there is a significant savings both in terms of reduced waste of the conductive precursor gas 105 and also reduced processing time to form conductive layers 160 of a desired thickness using the CVD deposition technique 100 described herein.
- FIG. 3B is a diagram which illustrates the advantages of using both a conductive precursor gas 105 and a reactant gas 107 in forming conductive layers 160 .
- FIG. 3B is a chart that is illustrative of the Resistivity (Rs) of films of either Pt or PtRh with multiple deposition steps.
- the total deposition time for the process illustrated in FIG. 3B is 300 seconds where the conductive precursor gas 105 is introduced for 50 seconds in combination with the reactant 107 and then for 10 seconds the reactant 107 is maintained by itself in the chamber 101 .
- there is a significant decrease in the resistivity which is indicative of an increase in the thickness of the film as compared to a single step, 300 second deposition without the introduction of a reactant 107 .
- the conductive precursor gas 105 is introduced simultaneously with the reactant 107 and then the reactant 107 is introduced for a limited period of time by itself to improve the deposition rate of the process.
- the system can either have the combined conductive precursor gas 105 /reactant 107 introduced for a selected time period followed by introduction of the reactant 107 alone for a selected time period or the system can monitor the rate of absorption of the conductive precursor gas 105 and, when it falls below a desired threshold, increase the concentration or change the composition of the reactant 107 which can then be followed by reintroduction of the conductive precursor gas 105 .
- a CVD system 200 includes a CVD chamber 201 that receives the conductor precursor gas 205 from a bubbler 204 wherein the bubbler 204 is supplied with the conductive carrier gas 203 from the conductive carrier gas source 202 in the previously described manner.
- the reactant 207 is introduced into the CVD chamber 201 from a reactant source 206 and waste gas 211 is supplied to a waste gas receptacle 210 in the previously described manner.
- a controller 212 such as a microprocessor, controls the operation of the CVD system 200 .
- the controller 212 receives a signal from the waste gas receptacle 210 that is indicative of the quantity of the conductive precursor gas 205 that is not being deposited onto or absorbed by the conductive layer 160 of the semiconductor device 150 and is, thus, being received by the waste gas receptacle 210 .
- a mass spectrometer can be installed in the waste gas receptacle 210 so as to provide an indication of the quantity of the conductive precursor gas 205 that is not being deposited onto the conductive layer 160 .
- This signal can then be used by the controller 212 to determine when to deliver the reactant 107 into the CVD chamber 201 .
- the signal can also be used to determine the appropriate composition of the reactant(s) 107 to be supplied to the CVD chamber 201 .
- FIG. 5 is a flow chart illustrating an exemplary manner of operation of the CVD system 200 of FIG. 4 .
- the semiconductive device 150 is initially positioned, in state 302 , within the CVD chamber 201 .
- the conductive precursor gas 105 is introduced, in state 304 , into the CVD chamber 201 .
- the conductive precursor gas 105 can be introduced in state 304 alone or in combination with the reactant 107 as discussed previously.
- the controller 212 can then determine, in decision state 306 , whether the absorption rate, indicative of the proportion of the conductive precursor gas 105 being deposited to form the conductive layer 160 , is above a preselected absorption rate. This determination can be based upon analysis of the conductive precursor gas 105 being received by the waste gas receptacle 210 as described above.
- the controller 212 determines, in decision state 306 , that the absorption rate is above a preselected threshold, the conductive precursor gas 105 continues to be supplied into the CVD chamber 201 in state 304 . However, if the controller 212 determines, in decision state 306 , that the absorption rate has decreased below the preselected threshold, the controller 212 then determines, in decision state 310 , whether the conductive layer 160 is at a desired thickness. The controller 212 can, for example, make this determination by comparing the elapsed time of the deposition cycle to empirically determined deposition rates for the particular conductive precursor gas 105 .
- the process then proceeds to an end state 314 allowing the semiconductor device 150 to be removed from the CVD chamber 201 . It will be appreciated that it may be desirable to introduce the reactant 107 into the CVD chamber 201 prior to removal of the semiconductor device 150 from the CVD chamber 201 so as to remove at least some of the organic compounds 162 prior to a subsequent processing step.
- the controller 212 can, in state 312 , then cease delivery of the conductive precursor gas 105 into the CVD chamber 201 and provide only the reactant 107 into the CVD chamber 201 for a predetermined period of time to enhance the removal of the organic compounds 162 in the conductive layer 160 . Subsequently, the conductive precursor gas 105 can be reintroduced into the CVD chamber 201 , in state 304 , for a subsequent deposition of the conductive layer 160 . In this way, intelligent control of the CVD system 200 can be obtained thereby resulting in more efficient chemical vapor deposition of conductive layers 160 and structures onto the semiconductor device 150 .
- the above-described process illustrates a manner of forming a conductive layer 160 or structure on a semiconductor device 150 that results in more efficient use of conductive precursor gas 105 .
- the improved efficiencies can also result in faster formation of the conductive layers 160 resulting in improved manufacturing efficiencies.
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Abstract
A technique for more efficiently forming conductive elements, such as conductive layers and electrodes, using chemical vapor deposition. A conductive precursor gas, such as a platinum precursor gas, having organic compounds to improve step coverage is introduced into a chemical vapor deposition chamber. A reactant is also introduced into the chamber that reacts with residue organic compounds on the conductive element so as to remove the organic compounds from the nucleating sites to thereby permit more efficient subsequent chemical vapor deposition of conductive elements.
Description
- This is a divisional application of U.S. patent application Ser. No. 10/757,638, filed on Jan. 13, 2004 which is a continuation application of U.S. patent application Ser. No. 10/234,729, filed Aug. 30, 2002, now U.S. Pat. No. 6,676,756, which was a divisional application of U.S. patent application Ser. No. 09/945,567 which was filed Aug. 30, 2001, now U.S. Pat. No. 6,576,538, all of which are hereby incorporated by reference in their entirety.
- 1. Field of the Invention
- The present invention relates to semiconductor processing and, in particular, concerns a metalorganic chemical vapor deposition (MOCVD) technique for forming component layers, such as platinum layers, in a manner that results in more efficient deposition of the component layer onto the surface of a semiconductor device.
- 2. Description of the Related Art
- Semiconductor processing techniques have become increasingly more complex as a result of the increasing density and smaller sizes of semiconductor devices. One particular problem that occurs with smaller sized semiconductor devices is that it is often difficult to form components, such as conductors, vias and electrodes, that conformally cover the contours of the semiconductor device. For example, a typical device formed by semiconductor processing is a capacitor. Typically, a capacitor is formed in an opening in an isolation layer of a semiconductor device and has two electrodes that are positioned within the opening with a dielectric separating the electrodes so as to cover both the side walls and the bottom floor of the opening. It will be appreciated that as the openings become smaller and smaller in size, it is increasingly more difficult to have the electrode formed so as to uniformly cover the side walls and bottom walls of the opening. Three dimensional capacitors are but one example of a device that is increasingly more difficult to fabricate due to decreasing device dimensions leading to difficulties with conformal covering of the device surface. Other devices in which this problem occurs include vias, electrodes and conductive lines.
- To address the particular problems associated with forming electrodes and other conductive elements on 3-dimensional surfaces, various techniques using various materials have been developed. One particularly common technique for forming three dimensional conductive elements, vias and lines in semiconductor applications is to use Chemical Vapor Deposition (CVD) techniques to deposit a conductive material, such as platinum (Pt), within an opening formed to contain a 3-dimensional conductive element.
- For example, platinum is viewed as an ideal electrode material for high-K capacitors in DRAM applications due to its relatively high work function. This high work function forms an increased energy barrier inhibiting leakage migration of charge carriers between electrodes through an intervening dielectric. Moreover, platinum is also generally not oxidizable such that the electrode's resistivity is not increased as a result of exposure to oxygen containing compounds contained within the semiconductor environment.
- Further, platinum is also strongly favored for formation of electrodes and 3-dimensional semiconductor structures, such as capacitors, conductors, vias and the like, due to its particularly advantageous step coverage when applied using chemical vapor deposition (CVD) techniques. In particular, platinum can be used to coat 3-dimensional structures through chemical vapor deposition such that the vertical side walls and the horizontal bottom surfaces are adequately covered by the deposited platinum.
- Typically, a platinum precursor and other reactants are introduced into the CVD chamber and the platinum carried by a precursor gas is then deposited onto the surface of the semiconductor substrate through thermal decomposition or reaction with another reactant gas, such as O2, N2O, or H2. The platinum is carried in the precursor gas, that often comprises an organic compound. The platinum atom is bonded to the organic compound to permit the platinum atoms to be transferred in the gas phase. This enables the Pt to be conformally deposited over the surface of the wafer as the organic compound facilitates improved step coverage.
- In the prior art, there is generally only a single deposition step such that the precursor gas and other reactant gas(es) are flowed into the CVD chamber until enough platinum, carried by the precursor gas, has been deposited on the exposed surface to form an electrode or other conductive element of a desired thickness. However, current CVD platinum deposition techniques have particularly low deposition efficiency such that the deposition rate is very slow, on the order of 1 Angstrom per second. In order to obtain a 300 Angstrom film, the deposition time is therefore usually several minutes. The relatively slow deposition rate creates inefficiencies in the manufacturing of semiconductor devices.
- Moreover, the platinum precursor gas used for deposition is particularly expensive, on the order of $100 per gram. It has been observed that typical CVD platinum deposition techniques result in enormous waste of this expensive platinum precursor gas as only a small proportion of the platinum carried by the precursor gas is actually being deposited on the semiconductor wafer positioned in the CVD chamber. Hence, not only are current CVD platinum deposition techniques slow, they are also particularly inefficient in delivering platinum to the wafer. This results in considerable waste of expensive material and increases the cost of manufacturing semiconductor devices that require 3-dimensional conductive structures, like electrodes or conductors.
- Further, the deposition process also results in the possible deposition of hydrocarbon byproducts on the surface of the semiconductor device which can become incorporated into or adsorbed onto the surface of the deposited film contaminating the film and inhibiting further deposition. In particular, the deposition of platinum in one typical process proceeds by the formula:
(C5H5)Pt(CH3)3+H2→Pt(film)+CH4+other hydrocarbons - The other hydrocarbons may not be volatile enough at the deposition temperature and thus stay on the surface of the film following deposition. This can result in contamination of the film and inhibit further deposition of the platinum film.
- From the foregoing, it will be appreciated that there is a need for an improved technique for depositing conductive materials onto a semiconductor surface such that good step coverage can be obtained without a significant increase in the cost of manufacturing the semiconductor device. To this end, there is a need for a more efficient way of depositing conductive material, such as platinum, in a manner that results in more efficient deposition of the material with less waste of the precursor material used to form the material.
- The aforementioned needs are satisfied by the present invention which, in one aspect, comprises a method of forming a conductive layer comprising (a) positioning a semiconductor device within a CVD chamber, (b) exposing the semiconductor device to a precursor gas containing a conductive element and a reactant to form the conductive layer for a first period of time, (c) exposing the semiconductor substrate to a reactant so that the reactant reacts with organic compounds contained within the conductive layer, and (d) reintroducing the precursor gas into the CVD chamber following exposure of the semiconductor substrate to the reactant so as to further form the conductive layer on the semiconductor device.
- In one particular embodiment, a semiconductor device with a defined opening for a 3-dimensional capacitor is positioned within a CVD chamber and is exposed to a precursor gas containing platinum which is then deposited using chemical vapor deposition techniques. A reactant is also introduced into the CVD chamber wherein the deposited platinum material is exposed to the reactant. The reactant can comprise any of a number of elements, compounds or processes, such as, for example, the introduction of a gas such as H2, N2O, NO, H2O, O2, ozone, or some other oxygen containing ambient, into the CVD chamber or with the enhancement of plasma or UV light. Moreover, the conductor can comprise not only platinum, but also other conductive films such as Ir, Rh, Ni, Co, Cu, W, and the like.
- In one embodiment, the reactant gas is introduced at the same time as the conductive precursor gas. In another embodiment, the reactant gas is introduced following the introduction of the precursor gas for a selected period of time. In either circumstance, the reactant gas reacts with the residual organic compounds so as to remove the residual organic compounds in or on the surface of the deposited films thereby increasing the deposition efficiency.
- Organic by-products can be adhered to the exposed surface of the deposited conductive layer. By introducing a reactant into the CVD chamber, the organic compounds can be removed by reaction with the reactants thereby making available more conductor nucleating sites and allowing greater absorption of the conductor precursor in the vapor phase.
- In another aspect of the invention, a system for forming a conductive layer on a semiconductor device is provided. In this aspect, the system includes a CVD chamber which receives the semiconductor device; a metal organic precursor gas source which provides a metal organic precursor gas with entrained conductive particles; a reactant source that provides a reactant to the CVD chamber and a controller which controls the delivery of conductive precursor gas and reactant into the CVD chamber. In this aspect, the controller allows for the delivery of the conductive precursor gas and the reactant into the chamber. The reactant is selected to react with organic compounds of the conductive precursor gas so as to remove the organic compound from the formed conductive layer. Hence, by delivering both the precursor and the reactant, either simultaneously or sequentially or both, the efficiency of the deposition process can be improved.
- In one particular embodiment, the system includes a sensor, such as, for example, a mass spectrometer, that provides a signal to the controller indicative of the deposition of the conductive precursor gas by the semiconductor device. When the deposition drops below a particular threshold, such that there is increased waste of the conductive precursor gas, the controller then induces the delivery of the reactant into the chamber.
- It will be appreciated that the aforementioned aspects of the present invention allow for more efficient formation of conductive layers with more efficient deposition of conductive material at a greater cost saving. These and other objects and advantages of the present invention will become more fully apparent from the following description taken in conjunction with the accompanying drawings.
-
FIG. 1 is a block diagram of one embodiment of a system for forming a conductive structure on a semiconductor device; -
FIGS. 2A-2C are cross-sectional views of a semiconductor device illustrating one embodiment of a method by which a conductive structure is formed on the device; -
FIG. 3A is an illustration of a typical platinum precursor gas molecule used in a CVD process; -
FIG. 3B is a chart illustrating the improved absorption characteristics of the process of the illustrated embodiments; -
FIG. 4 is a block diagram illustrating another embodiment of a system for forming a conductive structure on a semiconductor device; and -
FIG. 5 is a flow chart illustrating one method of forming a conductive structure on a semiconductor device. - Reference will now be made to the drawings wherein like numerals refer to like parts throughout. FIG. I is a block diagram which illustrates one example of a
system 100 for depositing a conductive layer on a semiconductor device in accordance with the illustrated embodiment. As is illustrated inFIG. 1 , aCVD chamber 101 of a type known in the art, is provided with aconductive precursor gas 105 that is used to deposit conductive layers and structures on semiconductor devices positioned within theCVD chamber 101. In particular, aconductive carrier gas 103 containing conductive elements is provided by a conductivecarrier gas source 102 and theconductive carrier gas 103 is supplied to abubbler 104 that contains a liquid precursor. Theconductive carrier gas 103 and the liquid precursor bind so as to allow the conductive element to be carried in a gas form in theconductive precursor gas 105 into theCVD chamber 101 so as to permit CVD coverage of the semiconductor devices in a manner known in the art. - In one particular embodiment, the
conductive carrier gas 103 is a known platinum-based carrier gas, such as platinum entrained in N2O. Theconductive carrier gas 103 is supplied to thebubbler 104 which, in this embodiment, contains a liquid methyl based precursor such that theconductive precursor gas 105 is comprised of (methylcyclopentadienyl) (trimethyl) platinum (MeCpPtMe3). The use of the organic methyl compound in theconductive precursor gas 105 allows for better step coverage during CVD deposition than just supplying a platinum carrier gas directly into theCVD chamber 101. As will be described in greater detail below, in one embodiment, theconductor precursor gas 105 is supplied to theCVD chamber 101 for a preselected period of time so as to allow the conductive element to coat the semiconductor device via chemical vapor deposition (CVD) techniques. - While in this embodiment, the
conductive precursor gas 105 is a Platinum conductive gas, it will be appreciated that any of a number of different precursor gases used to form conductive films can be used without departing from the present invention. These gases include gases that entrain conductive elements such as Ir, Rh, Ni, Co, Cu, W, and the like. - As is also illustrated in
FIG. 1 , thesystem 100 includes areactant source 106 that provides areactant 107 into theCVD chamber 101 that is selected so as to interact with the organic compounds of theconductive precursor gas 105 to thereby facilitate more efficient deposition of the conductive elements contained within theconductive precursor gas 105. In one particular embodiment, thereactant source 106 provides thereactant 107 selected from the group comprising NH3, H2, N2, NO, N2O, O2, O3, or any other O containing ambient. Providing thereactant 107 into theCVD chamber 101 allows the conductive elements contained within theconductive precursor gas 105 to deposit on the surface of the semiconductor device. Providing thereactant 107 into theCVD chamber 101, also results in thereactant 107 reacting with residual organic compounds or other contaminants from theconductive precursor gas 105 that have been deposited on the conductive structure formed during the CVD step thereby allowing for more efficient deposition of conductive elements during subsequent chemical vapor deposition steps. As is also illustrated inFIG. 1 , the illustratedsystem 100 also includes awaste gas receptacle 110 that receiveswaste gas 111 comprised of unusedconductive precursor gas 105 andunused reactants 107 during the process. - In the preferred process, the
reactant 107 and theconductive precursor gas 105 are simultaneously introduced into theCVD chamber 101 for a period of time that is selected to obtain a resulting conductive film of a desired thickness. When both thereactant 107 and theconductive precursor gas 105 are introduced into thechamber 101, thereactant 107 reacts with the contaminants contained within the film that may not otherwise be volatile enough at the deposition temperature and stay on the surface. - In one embodiment, the
reactant 107 is an oxidizing agent, such as NO, N2O, O2, or O3, that reacts with the organic byproducts on the surface to give them sufficient energy to become a gas that can be removed as thewaste gas 111. In other embodiments, thereactant 107 is a reducing agent such as NH3 or H2. In the specific application of using platinum, platinum is an active catalyst that absorbs hydrogen at its surface and it activates the molecules enough to react with carbon or methyl (CH3) to form CH4 and other hydrocarbons. The introduction of thereactant 107 helps to remove these other hydrocarbons. - In the preferred embodiment, the
reactant 107 and theconductive precursor gas 105 are introduced into thechamber 101 simultaneously until a film of a desired thickness is achieved. It will, however, be appreciated that theprecursor gas 105 and thereactant gas 107 can be introduced sequentially until a film of a desired thickness is achieved without departing from the spirit of the present invention. It should be appreciated that introduced should be construed to mean both initiating the supply of an agent and also continuing to supply that agent for some period of time. -
FIGS. 2A-2C schematically illustrate the process of the illustrated embodiment in greater detail. More particularly,FIGS. 2A-2C provide a simplified illustration of how aconductive layer 160, such as a lower electrode of a capacitor or a conductive, would be formed in anopening 156 that is adapted to receive, for example, a capacitor. As is illustrated inFIG. 2A , asemiconductor device 150, which can comprise asemiconductor substrate 152 with an insulatinglayer 154 positioned thereon, is positioned within theCVD chamber 101. In this particular simplified example, thesemiconductor device 150 includes theopening 156 formed in the insulatinglayer 154 which is then to be coated with theconductive layer 160. - As is illustrated in
FIG. 2A , theconductive precursor gas 105 is introduced into theCVD chamber 101 such that a conductive material, such as platinum, is deposited on the exposed surfaces of thesemiconductor device 150. Using theconductive precursor gas 105 illustrated inFIG. 4 results in a relatively high degree of step coverage of theconductive layer 160 on the horizontal surfaces and also on the vertical side wall surfaces of thesemiconductor device 150. As is also schematically represented inFIG. 2A , the initial deposition of theconductive layer 160 results inorganic compounds 162 occupying the surface nucleating sites of theconductive layer 160. In particular, for theconductive precursor gas 105 illustrated inFIG. 3A , theorganic compound 162 that comprises the methyl molecules poisons the exposed surface of theconductive layer 160 by covering the available platinum nucleating sites or by otherwise inhibiting further absorption of theconductive precursor gas 105 in the vapor phase. - As is also schematically illustrated in
FIG. 2A , thereactant 107 is introduced into theCVD chamber 101 as theconductive precursor gas 105. Thereactant 107 preferably reacts with theorganic compounds 162 thereby removing these compounds in the previously described manner to improve the deposition efficiency of the process. The process illustrated inFIG. 2A can thus be continued until aconductive layer 160 of a desired thickness is achieved. The simultaneous introduction of theconductive precursor gas 105 and thereactant 107 results in more efficient deposition as is illustrated in the chart ofFIG. 3B discussed hereinbelow. - As was also discussed above, the
reactant 107 can also be introduced after theconductive precursor gas 105 has been introduced for a set period of time in the manner shown inFIG. 2B . Specifically, theconductive precursor gas 105 can be initially introduced and thereactant 107 can then be introduced subsequently to remove thecontaminants 162 and theconductive precursor gas 105 can then be reintroduced again. - For example, once the
conductive layer 160 is no longer efficiently absorbing the conductive elements of theconductive precursor gas 105, the flow of theconductive precursor gas 105 into theCVD chamber 101 is stopped and thesemiconductor device 150 within theCVD chamber 101 is then exposed to areactant 107 from thereactant source 106. Preferably, thereactant source 106 is selected to provide areactant 107 that reacts with theorganic compounds 162 of theconductive precursor gas 105 so as to remove at least some of theorganic compounds 162 from conductive element nucleation sites within theconductive layer 160. In certain embodiments, thereactant 107, as introduced subsequent to cessation of introduction of theconductive precursor gas 105, comprises areactant 107 selected from the group comprising N2O, O2, H2, NH3, NO, H2O, ozone, vacuum, and inert gas purge, such as with N2 or argon. In certain embodiments, thereactant 107 also comprises providing supplemental plasma treatment and/or UV light to theCVD chamber 101. - It will be appreciated that in certain embodiments, the
reactant 107 as introduced with theconductive precursor gas 105 comprises thesame reactant 107 as introduced absent the introduction of theconductive precursor gas 105. In other embodiments, thereactant 107 as introduced absent the introduction of theconductive precursor gas 105 comprises alternative or additional components as thereactant 107 as introduced with theconductive precursor gas 105. - As illustrated in
FIG. 2C , subsequent to the exposure of theconductive layer 160 to thereactant 107, thereactant source 106 stops providing thereactant 107 into theCVD chamber 101 and theconductive precursor gas 105 is again provided into theCVD chamber 101 in the previously described manner. This results in further deposition of the conductive elements contained within theconductive precursor gas 105 so as to result in greater deposition of the conductive elements. Since thereactant 107 has removed at least some of theorganic compounds 162 from theconductive layer 160 that would otherwise inhibit further chemical vapor deposition of the conductive elements of theconductive precursor gas 105, more conductive elements can be added to theconductive layer 160 by a subsequent chemical vapor deposition step. - Hence, the process of forming the
conductive layer 160 in this embodiment can either comprise introducing aconductive precursor gas 105 and areactant 107 simultaneously into theCVD chamber 101 for a preselected period of time to form a conductive structure or sequentially introducing aconductive precursor gas 105 and areactant 107 to form theconductive structure 160. - In one particular example, a
conductive layer 160 is formed using an initial deposition step wherein a platinum precursor carrier gas is provided from the conductivecarrier gas source 102 through thebubbler 104 at a rate of between 40 to 200 sccm with the platinum being encapsulated within a helium carrier. Thebubbler 104 contains a liquid precursor at a temperature between 35° C. and 50° C., such that the resultingconductive precursor gas 105 emanating from thebubbler 104 has the chemical composition as illustrated inFIG. 3A . The resultingconductive precursor gas 105 is provided from thebubbler 104 to theCVD chamber 101 along with a simultaneous flow of N2O reactant 107 at a rate of 100 to 800 sccm from thereactant source 106. This flow ofconductive precursor gas 105 andreactant 107 is provided to theCVD chamber 101 for approximately 50 seconds to result in deposition of theconductive layer 160. At the end of the 50 second period, the flow of theconductive precursor gas 105 from thebubbler 104 is ceased while the flow of the N2O reactant 107 from thereactant source 106 is continued for 10 seconds. The N2O thus comprises thereactant 107 which reacts with theorganic compounds 162 in the depositedlayer 160 associated with theconductive precursor gas 105 so as to remove theorganic compounds 162 from the deposited,conductive layer 160 in the manner described in conjunction withFIG. 2B . - Subsequently, the
conductive precursor gas 105 is provided for another 50 second interval and is then followed by a 10 second exposure of theconductive layer 160 to the N2O reactant 107 from thereactant source 106. This process is repeated until aconductive layer 160 of a desired thickness is formed. - Repeating the above-described exemplary process for three iterations results in the deposition of a platinum
conductive layer 160 that has a resistivity of approximately 1.1 Ohm/sq. With the same processing parameters and devices, a single step CVD deposition that does not include either simultaneous or sequential introduction ofreactant 107 for the same overall duration results in a conductive layer having a resistivity on the order of 170 hm/sq. - It will be understood that resistivity of the deposited
conductive layer 160 is inversely proportional to the thickness of theconductive layer 160 which indicates that there is a very significant increase in the deposition rate of the film using the process of the above-described embodiment. In fact, the Applicant has observed at least ten-fold increases in the deposition rate over known CVD deposition techniques for conductive layers of this type. Hence, there is a significant savings both in terms of reduced waste of theconductive precursor gas 105 and also reduced processing time to formconductive layers 160 of a desired thickness using theCVD deposition technique 100 described herein. -
FIG. 3B is a diagram which illustrates the advantages of using both aconductive precursor gas 105 and areactant gas 107 in formingconductive layers 160.FIG. 3B is a chart that is illustrative of the Resistivity (Rs) of films of either Pt or PtRh with multiple deposition steps. The total deposition time for the process illustrated inFIG. 3B is 300 seconds where theconductive precursor gas 105 is introduced for 50 seconds in combination with thereactant 107 and then for 10 seconds thereactant 107 is maintained by itself in thechamber 101. As is illustrated, there is a significant decrease in the resistivity which is indicative of an increase in the thickness of the film as compared to a single step, 300 second deposition without the introduction of areactant 107. - In the specific example described above, the
conductive precursor gas 105 is introduced simultaneously with thereactant 107 and then thereactant 107 is introduced for a limited period of time by itself to improve the deposition rate of the process. It will be appreciated that the system can either have the combinedconductive precursor gas 105/reactant 107 introduced for a selected time period followed by introduction of thereactant 107 alone for a selected time period or the system can monitor the rate of absorption of theconductive precursor gas 105 and, when it falls below a desired threshold, increase the concentration or change the composition of thereactant 107 which can then be followed by reintroduction of theconductive precursor gas 105. - For example, as is illustrated in
FIG. 4 , aCVD system 200 includes aCVD chamber 201 that receives theconductor precursor gas 205 from abubbler 204 wherein thebubbler 204 is supplied with theconductive carrier gas 203 from the conductivecarrier gas source 202 in the previously described manner. Similarly, thereactant 207 is introduced into theCVD chamber 201 from areactant source 206 andwaste gas 211 is supplied to awaste gas receptacle 210 in the previously described manner. Acontroller 212, such as a microprocessor, controls the operation of theCVD system 200. Moreover, thecontroller 212 receives a signal from thewaste gas receptacle 210 that is indicative of the quantity of theconductive precursor gas 205 that is not being deposited onto or absorbed by theconductive layer 160 of thesemiconductor device 150 and is, thus, being received by thewaste gas receptacle 210. For example, a mass spectrometer can be installed in thewaste gas receptacle 210 so as to provide an indication of the quantity of theconductive precursor gas 205 that is not being deposited onto theconductive layer 160. This signal can then be used by thecontroller 212 to determine when to deliver thereactant 107 into theCVD chamber 201. The signal can also be used to determine the appropriate composition of the reactant(s) 107 to be supplied to theCVD chamber 201. -
FIG. 5 is a flow chart illustrating an exemplary manner of operation of theCVD system 200 ofFIG. 4 . From astart state 300 thesemiconductive device 150 is initially positioned, instate 302, within theCVD chamber 201. Subsequently, theconductive precursor gas 105 is introduced, instate 304, into theCVD chamber 201. Theconductive precursor gas 105 can be introduced instate 304 alone or in combination with thereactant 107 as discussed previously. - The
controller 212 can then determine, indecision state 306, whether the absorption rate, indicative of the proportion of theconductive precursor gas 105 being deposited to form theconductive layer 160, is above a preselected absorption rate. This determination can be based upon analysis of theconductive precursor gas 105 being received by thewaste gas receptacle 210 as described above. - If the
controller 212 determines, indecision state 306, that the absorption rate is above a preselected threshold, theconductive precursor gas 105 continues to be supplied into theCVD chamber 201 instate 304. However, if thecontroller 212 determines, indecision state 306, that the absorption rate has decreased below the preselected threshold, thecontroller 212 then determines, indecision state 310, whether theconductive layer 160 is at a desired thickness. Thecontroller 212 can, for example, make this determination by comparing the elapsed time of the deposition cycle to empirically determined deposition rates for the particularconductive precursor gas 105. If thecontroller 212 determines, indecision state 310, that the thickness of theconductive layer 160 is the desired thickness, the process then proceeds to anend state 314 allowing thesemiconductor device 150 to be removed from theCVD chamber 201. It will be appreciated that it may be desirable to introduce thereactant 107 into theCVD chamber 201 prior to removal of thesemiconductor device 150 from theCVD chamber 201 so as to remove at least some of theorganic compounds 162 prior to a subsequent processing step. - However, if the absorption rate has dropped below the optimum and the
conductive layer 160 is not at the desired thickness, thecontroller 212 can, instate 312, then cease delivery of theconductive precursor gas 105 into theCVD chamber 201 and provide only thereactant 107 into theCVD chamber 201 for a predetermined period of time to enhance the removal of theorganic compounds 162 in theconductive layer 160. Subsequently, theconductive precursor gas 105 can be reintroduced into theCVD chamber 201, instate 304, for a subsequent deposition of theconductive layer 160. In this way, intelligent control of theCVD system 200 can be obtained thereby resulting in more efficient chemical vapor deposition ofconductive layers 160 and structures onto thesemiconductor device 150. - From the foregoing, it will be appreciated that the above-described process illustrates a manner of forming a
conductive layer 160 or structure on asemiconductor device 150 that results in more efficient use ofconductive precursor gas 105. This results in significantly less waste of theconductive precursor gas 105 resulting in cost savings for the manufacturing process. Moreover, the improved efficiencies can also result in faster formation of theconductive layers 160 resulting in improved manufacturing efficiencies. - Although the foregoing description of the preferred embodiment of the present invention has shown, described and pointed out the fundamental novel features of the invention, it will be understood that various omissions, substitutions and changes in the form of the detail of the apparatus as illustrated as well as the uses thereof, may be made by those skilled in the art without departing from the spirit of the present invention. Consequently, the scope of the present invention should not be limited to the foregoing discussions, but should be defined by the appended claims.
Claims (10)
1. A system for forming a conductive element on a semiconductor device, the system comprising:
a chamber that receives the semiconductor device;
a conductive precursor gas supply system that provides a conductive precursor gas to the chamber wherein the conductive precursor gas has both conductive components that when deposited on the semiconductor device form the conductive element and organic components that facilitate step coverage of the conductive element over the semiconductor device;
a reactant supply system that introduces a reactant into the chamber that is selected to enable deposition of the conductive components of the conductive precursor gas on the semiconductor device and to remove organic components off of the conductive element to facilitate further deposition of the conductive components of the conductive precursor gas on the conductive element; and
a controller that monitors the rate of deposition of the conductive components and controls the delivery of the conductive precursor gas and the reactant into the chamber, wherein the controller introduces the reactant into the chamber when the rate of deposition of the conductive components onto the semiconductor device falls below a pre-selected threshold.
2. The system of claim 1 , wherein the conductive precursor gas supply system includes a carrier gas supply device that supplies the conductive element in a gas form and a liquid precursor system that receives the carrier gas and produces the conductive precursor gas for delivery into the chamber.
3. The system of claim 2 , wherein the conductive precursor gas supply system provides a platinum precursor gas into the chamber.
4. The system of claim 3 , wherein the conductive precursor gas supply system provides a platinum precursor gas into the chamber wherein the platinum is bonded to a methyl compound so as to improve step coverage of the platinum when forming the conductive element.
5. The system of claim 4 , wherein the conductive precursor gas supply system introduces a (methylcyclopentadienyl)(trimethyl) platinum gas into the chemical vapor deposition chamber.
6. The system of claim 1 , wherein the reactant supply system introduces a reactant selected from the group comprising N2O, O2, NH3, NO, H2O, ozone, plasma, vacuum, inert gas, and UV light.
7. The system of claim 1 , further comprising a waste receptacle that receives waste conductive precursor gas following introduction of the waste conductive precursor gas into the chamber and wherein the controller determines whether to introduce the reactant gas based upon the constituent components of the gas receives in the waste receptacle.
8. The system of claim 7 , further comprising a sensor positioned within the waste receptacle that provides a signal indicative of the rate of deposition of the conductive element of the conductive precursor gas on the semiconductor device during formation of the conductive element.
9. The system of claim 8 , wherein the sensor provides the controller with a signal indicative of the amount of conductive element being transmitted to the waste receptacle following introduction into the chamber such that when the amount of conductive element in the waste receptacle exceeds a pre-selected threshold, the controller can introduce the reactant into the chamber to reduce the build up of non-conductive components on the conductive element.
10. The system of claim 9 , wherein the sensor comprises a mass spectrometer.
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KR100442963B1 (en) * | 2001-12-29 | 2004-08-04 | 주식회사 하이닉스반도체 | Method of manufacturing metal layer having high degree of purity |
DE10348106A1 (en) * | 2003-10-16 | 2005-05-19 | Clariant Gmbh | Azo pigment preparations for packaging gravure and flexo printing |
US8158488B2 (en) | 2004-08-31 | 2012-04-17 | Micron Technology, Inc. | Method of increasing deposition rate of silicon dioxide on a catalyst |
JP5088363B2 (en) * | 2007-03-15 | 2012-12-05 | 富士通セミコンダクター株式会社 | Chemical vapor deposition apparatus, film forming method, and semiconductor device manufacturing method |
US7943527B2 (en) * | 2008-05-30 | 2011-05-17 | The Board Of Trustees Of The University Of Illinois | Surface preparation for thin film growth by enhanced nucleation |
US20100075037A1 (en) * | 2008-09-22 | 2010-03-25 | Marsh Eugene P | Deposition Systems, ALD Systems, CVD Systems, Deposition Methods, ALD Methods and CVD Methods |
US8753933B2 (en) * | 2008-11-19 | 2014-06-17 | Micron Technology, Inc. | Methods for forming a conductive material, methods for selectively forming a conductive material, methods for forming platinum, and methods for forming conductive structures |
FR2940980B1 (en) | 2009-01-15 | 2011-07-29 | Centre Nat Rech Scient | METAL COMPLEXES FOR PLATINUM VAPOR PHASE CHEMICAL DEPOSITION |
US8846146B2 (en) | 2010-11-01 | 2014-09-30 | The Board Of Trustees Of The University Of Illinois | Smoothing agents to enhance nucleation density in thin film chemical vapor deposition |
US9343749B2 (en) | 2013-05-29 | 2016-05-17 | Ford Global Technologies, Llc | Ultrathin platinum films |
US11584986B1 (en) | 2017-11-01 | 2023-02-21 | The Board Of Trustees Of The University Of Illinois | Area selective CVD of metallic films using precursor gases and inhibitors |
Citations (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5104684A (en) * | 1990-05-25 | 1992-04-14 | Massachusetts Institute Of Technology | Ion beam induced deposition of metals |
US5130172A (en) * | 1988-10-21 | 1992-07-14 | The Regents Of The University Of California | Low temperature organometallic deposition of metals |
US5204314A (en) * | 1990-07-06 | 1993-04-20 | Advanced Technology Materials, Inc. | Method for delivering an involatile reagent in vapor form to a CVD reactor |
US5322712A (en) * | 1993-05-18 | 1994-06-21 | Air Products And Chemicals, Inc. | Process for improved quality of CVD copper films |
US5403620A (en) * | 1992-10-13 | 1995-04-04 | Regents Of The University Of California | Catalysis in organometallic CVD of thin metal films |
US5552327A (en) * | 1994-08-26 | 1996-09-03 | North Carolina State University | Methods for monitoring and controlling deposition and etching using p-polarized reflectance spectroscopy |
US5576071A (en) * | 1994-11-08 | 1996-11-19 | Micron Technology, Inc. | Method of reducing carbon incorporation into films produced by chemical vapor deposition involving organic precursor compounds |
US5672385A (en) * | 1995-03-28 | 1997-09-30 | Anelva Corporation | Titanium nitride film-MOCVD method incorporating use of tetrakisdialkylaminotitanium as a source gas |
US5763007A (en) * | 1996-06-25 | 1998-06-09 | The Aerospace Corporation | Method of Controlling Reactions between tetrakis dialkylamine titanium and ammonia for producing titanium nitride films |
US5783716A (en) * | 1996-06-28 | 1998-07-21 | Advanced Technology Materials, Inc. | Platinum source compositions for chemical vapor deposition of platinum |
US5789027A (en) * | 1996-11-12 | 1998-08-04 | University Of Massachusetts | Method of chemically depositing material onto a substrate |
US5902651A (en) * | 1996-01-08 | 1999-05-11 | Micron Technology, Inc. | Method of reducing carbon incorporation into films produced by chemical vapor deposition involving titanium organometallic and metal-organic precursor compounds |
US5990559A (en) * | 1998-08-27 | 1999-11-23 | Micron Technology, Inc. | Circuitry comprising roughened platinum layers, platinum-containing materials, capacitors comprising roughened platinum layers, methods forming roughened layers of platinum, and methods of forming capacitors |
US6010744A (en) * | 1997-12-23 | 2000-01-04 | Advanced Technology Materials, Inc. | Method for nucleation controlled chemical vapor deposition of metal oxide ferroelectric thin films |
US6140230A (en) * | 1998-02-19 | 2000-10-31 | Micron Technology, Inc. | Methods of forming metal nitride and silicide structures |
US6146608A (en) * | 1997-11-24 | 2000-11-14 | Advanced Technology Materials, Inc. | Stable hydride source compositions for manufacture of semiconductor devices and structures |
US6180974B1 (en) * | 1996-12-06 | 2001-01-30 | Sharp Kabushiki Kaisha | Semiconductor storage device having a capacitor electrode formed of at least a platinum-rhodium oxide |
US6201271B1 (en) * | 1997-07-29 | 2001-03-13 | Sharp Kabushiki Kaisha | Semiconductor memory device prevented from deterioration due to activated hydrogen |
US6204172B1 (en) * | 1998-09-03 | 2001-03-20 | Micron Technology, Inc. | Low temperature deposition of barrier layers |
US20010000865A1 (en) * | 1999-07-08 | 2001-05-10 | National Semiconductor Corporation | Wafer produced by method of quality control for chemical vapor deposition |
US6271136B1 (en) * | 2000-04-04 | 2001-08-07 | Taiwan Semiconductor Manufacturing Company | Multi-step plasma process for forming TiSiN barrier |
US6271131B1 (en) * | 1998-08-26 | 2001-08-07 | Micron Technology, Inc. | Methods for forming rhodium-containing layers such as platinum-rhodium barrier layers |
US20010044207A1 (en) * | 1998-09-03 | 2001-11-22 | Micron Technology, Inc. | Direct writing of low carbon conductive material |
US20010043453A1 (en) * | 1999-12-30 | 2001-11-22 | Narwankar Pravin K. | Method of forming metal electrodes |
US6329286B1 (en) * | 1999-04-27 | 2001-12-11 | Micron Technology, Inc. | Methods for forming conformal iridium layers on substrates |
US6403414B2 (en) * | 1998-09-03 | 2002-06-11 | Micron Technology, Inc. | Method for producing low carbon/oxygen conductive layers |
US20020076492A1 (en) * | 1998-04-14 | 2002-06-20 | Cvd Systems, Inc. | Film processing system |
US20030100183A1 (en) * | 2001-11-28 | 2003-05-29 | Weimin Li | CVD of PtRh with good adhesion and morphology |
US6576538B2 (en) * | 2001-08-30 | 2003-06-10 | Micron Technology, Inc. | Technique for high efficiency metalorganic chemical vapor deposition |
US6605735B2 (en) * | 2001-09-12 | 2003-08-12 | Tosoh Corporation | Ruthenium complex, process for producing the same and process for producing thin film |
US6689700B1 (en) * | 1999-11-02 | 2004-02-10 | University Of Massachusetts | Chemical fluid deposition method for the formation of metal and metal alloy films on patterned and unpatterned substrates |
US6998152B2 (en) * | 1999-12-20 | 2006-02-14 | Micron Technology, Inc. | Chemical vapor deposition methods utilizing ionic liquids |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US43453A (en) * | 1864-07-05 | Improvement in wagon-brakes | ||
US44207A (en) * | 1864-09-13 | Improvement in locks | ||
US865A (en) * | 1838-08-01 | Improvement in fire-arms | ||
US76492A (en) * | 1868-04-07 | John w |
-
2001
- 2001-08-30 US US09/945,567 patent/US6576538B2/en not_active Expired - Lifetime
-
2002
- 2002-08-30 US US10/234,729 patent/US6676756B1/en not_active Expired - Lifetime
-
2004
- 2004-01-13 US US10/757,638 patent/US6921710B2/en not_active Expired - Fee Related
- 2004-01-13 US US10/756,222 patent/US7214618B2/en not_active Expired - Fee Related
-
2005
- 2005-06-07 US US11/146,953 patent/US20050223978A1/en not_active Abandoned
Patent Citations (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5130172A (en) * | 1988-10-21 | 1992-07-14 | The Regents Of The University Of California | Low temperature organometallic deposition of metals |
US5104684A (en) * | 1990-05-25 | 1992-04-14 | Massachusetts Institute Of Technology | Ion beam induced deposition of metals |
US5204314A (en) * | 1990-07-06 | 1993-04-20 | Advanced Technology Materials, Inc. | Method for delivering an involatile reagent in vapor form to a CVD reactor |
US5403620A (en) * | 1992-10-13 | 1995-04-04 | Regents Of The University Of California | Catalysis in organometallic CVD of thin metal films |
US5322712A (en) * | 1993-05-18 | 1994-06-21 | Air Products And Chemicals, Inc. | Process for improved quality of CVD copper films |
US5552327A (en) * | 1994-08-26 | 1996-09-03 | North Carolina State University | Methods for monitoring and controlling deposition and etching using p-polarized reflectance spectroscopy |
US5576071A (en) * | 1994-11-08 | 1996-11-19 | Micron Technology, Inc. | Method of reducing carbon incorporation into films produced by chemical vapor deposition involving organic precursor compounds |
US5672385A (en) * | 1995-03-28 | 1997-09-30 | Anelva Corporation | Titanium nitride film-MOCVD method incorporating use of tetrakisdialkylaminotitanium as a source gas |
US6162712A (en) * | 1995-06-30 | 2000-12-19 | Advanced Technology Materials, Inc. | Platinum source compositions for chemical vapor deposition of platinum |
US5902651A (en) * | 1996-01-08 | 1999-05-11 | Micron Technology, Inc. | Method of reducing carbon incorporation into films produced by chemical vapor deposition involving titanium organometallic and metal-organic precursor compounds |
US5763007A (en) * | 1996-06-25 | 1998-06-09 | The Aerospace Corporation | Method of Controlling Reactions between tetrakis dialkylamine titanium and ammonia for producing titanium nitride films |
US5783716A (en) * | 1996-06-28 | 1998-07-21 | Advanced Technology Materials, Inc. | Platinum source compositions for chemical vapor deposition of platinum |
US5789027A (en) * | 1996-11-12 | 1998-08-04 | University Of Massachusetts | Method of chemically depositing material onto a substrate |
US6180974B1 (en) * | 1996-12-06 | 2001-01-30 | Sharp Kabushiki Kaisha | Semiconductor storage device having a capacitor electrode formed of at least a platinum-rhodium oxide |
US6201271B1 (en) * | 1997-07-29 | 2001-03-13 | Sharp Kabushiki Kaisha | Semiconductor memory device prevented from deterioration due to activated hydrogen |
US6146608A (en) * | 1997-11-24 | 2000-11-14 | Advanced Technology Materials, Inc. | Stable hydride source compositions for manufacture of semiconductor devices and structures |
US6010744A (en) * | 1997-12-23 | 2000-01-04 | Advanced Technology Materials, Inc. | Method for nucleation controlled chemical vapor deposition of metal oxide ferroelectric thin films |
US6140230A (en) * | 1998-02-19 | 2000-10-31 | Micron Technology, Inc. | Methods of forming metal nitride and silicide structures |
US20020076492A1 (en) * | 1998-04-14 | 2002-06-20 | Cvd Systems, Inc. | Film processing system |
US6271131B1 (en) * | 1998-08-26 | 2001-08-07 | Micron Technology, Inc. | Methods for forming rhodium-containing layers such as platinum-rhodium barrier layers |
US5990559A (en) * | 1998-08-27 | 1999-11-23 | Micron Technology, Inc. | Circuitry comprising roughened platinum layers, platinum-containing materials, capacitors comprising roughened platinum layers, methods forming roughened layers of platinum, and methods of forming capacitors |
US6403414B2 (en) * | 1998-09-03 | 2002-06-11 | Micron Technology, Inc. | Method for producing low carbon/oxygen conductive layers |
US20010044207A1 (en) * | 1998-09-03 | 2001-11-22 | Micron Technology, Inc. | Direct writing of low carbon conductive material |
US6204172B1 (en) * | 1998-09-03 | 2001-03-20 | Micron Technology, Inc. | Low temperature deposition of barrier layers |
US6329286B1 (en) * | 1999-04-27 | 2001-12-11 | Micron Technology, Inc. | Methods for forming conformal iridium layers on substrates |
US20010000865A1 (en) * | 1999-07-08 | 2001-05-10 | National Semiconductor Corporation | Wafer produced by method of quality control for chemical vapor deposition |
US6689700B1 (en) * | 1999-11-02 | 2004-02-10 | University Of Massachusetts | Chemical fluid deposition method for the formation of metal and metal alloy films on patterned and unpatterned substrates |
US6998152B2 (en) * | 1999-12-20 | 2006-02-14 | Micron Technology, Inc. | Chemical vapor deposition methods utilizing ionic liquids |
US20010043453A1 (en) * | 1999-12-30 | 2001-11-22 | Narwankar Pravin K. | Method of forming metal electrodes |
US6475854B2 (en) * | 1999-12-30 | 2002-11-05 | Applied Materials, Inc. | Method of forming metal electrodes |
US6271136B1 (en) * | 2000-04-04 | 2001-08-07 | Taiwan Semiconductor Manufacturing Company | Multi-step plasma process for forming TiSiN barrier |
US6576538B2 (en) * | 2001-08-30 | 2003-06-10 | Micron Technology, Inc. | Technique for high efficiency metalorganic chemical vapor deposition |
US6605735B2 (en) * | 2001-09-12 | 2003-08-12 | Tosoh Corporation | Ruthenium complex, process for producing the same and process for producing thin film |
US20030100183A1 (en) * | 2001-11-28 | 2003-05-29 | Weimin Li | CVD of PtRh with good adhesion and morphology |
Also Published As
Publication number | Publication date |
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US6676756B1 (en) | 2004-01-13 |
US20040142559A1 (en) | 2004-07-22 |
US7214618B2 (en) | 2007-05-08 |
US20040147103A1 (en) | 2004-07-29 |
US6921710B2 (en) | 2005-07-26 |
US6576538B2 (en) | 2003-06-10 |
US20030049932A1 (en) | 2003-03-13 |
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