WO1997030476A1 - Chromium refractory metal alloys conductors for use in high temperature integrated circuits - Google Patents

Chromium refractory metal alloys conductors for use in high temperature integrated circuits Download PDF

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Publication number
WO1997030476A1
WO1997030476A1 PCT/US1997/002278 US9702278W WO9730476A1 WO 1997030476 A1 WO1997030476 A1 WO 1997030476A1 US 9702278 W US9702278 W US 9702278W WO 9730476 A1 WO9730476 A1 WO 9730476A1
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WO
WIPO (PCT)
Prior art keywords
thin film
film conductor
integrated circuit
chromium
high temperature
Prior art date
Application number
PCT/US1997/002278
Other languages
French (fr)
Inventor
George Gabriel Goetz
Warren Michael Dawson
Original Assignee
Alliedsignal Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Publication of WO1997030476A1 publication Critical patent/WO1997030476A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
    • H01L23/53257—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being a refractory metal
    • 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
    • H01L21/76801—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 dielectrics, e.g. smoothing
    • H01L21/76829—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 dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
    • H01L21/76834—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 dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers formation of thin insulating films on the sidewalls or on top of conductors
    • 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
    • H01L21/76885—By forming conductive members before deposition of protective insulating material, e.g. pillars, studs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • This invention relates to high temperature electronics and more particularly to metal alloy conductors for use in high temperature semi ⁇ conductor integrated circuit electronics.
  • J current densities
  • MTTF mean time to failure
  • Aluminum is clearly the present metal of choice for IC conductors. It provides low resistivity, resistance to corrosion, and with proper processing an excellent step coverage over non smooth surface morphology. However, the same basic property which permits good step coverage, tntra-atom bonds that are relatively easily broken, makes a material more susceptible to electromigration. While aluminum films are sufficiently stable to yield acceptable life in most power ICs at 125°C, there are serious life problems well below 200°C. Considerable effort has been expended to increase the high current density life of aluminum films through the addition of small percentages of other elements. Increases in life by over an order of magnitude have been reported with several different additions. However, the addition of other elements are also associated with increases in resistivity of the conductor.
  • the second metalization scheme used titanium tungsten (TiW) which was also passivated with a conformal SijN coating after patterning and which
  • the present invention provides for improved conductors; for use in high temperature semiconductor integrated circuit electronics, which utilized chromium refractory metal alloys.
  • the preferred combination for a high temperature thin film conductor with desirable properties are alloys of tungsten (W) with chromium (Cr).
  • the tungsten chromium combination is deposited and etched to form the desired interconnections and contacts on an integrated circuit. When the deposited CrW thin film conductor is heated in an appropriate atmosphere some chromium diffuses to the surface and oxidizes.
  • FIG. 1 is a section view of a CrW thin film conductor according to the present invention
  • FIG. 2 is a section view, similar to FIG. 1, taken in Fig. 3 along the line II - ⁇ prior to passivation;
  • FIG. 3 is a perspective view of a portion of an integrated circuit showing some exemplary interconnect line conductors.
  • FIG. 4 shows a CrW alloy deposited on an integrated circuit surface prior to etching to form the patterned interconnections lines.
  • FIG. 1 a cross section of a thin film CrW conductor 14 according to the present invention, suitable for use in high temperature semiconductor integrated circuit electronics.
  • the thin file conductor 14 is formed by depositing a CrW alloy layer 8, as shown in FIG. 4, on a layer 12 which will form part of an integrated circuit.
  • the thin -4- film passivated CrW conductor 14 can be formed by depositing on layer 12 the thin film CrW layer 8 by means well known in the art such as sputtering, simultaneous E-beam vacuum evaporation, or the like.
  • the CrW alloy layer 8 is then etched to form the desired pattern of interconnection lines 10 as shown in FIG. 3.
  • the layer on which conductor 14 is formed can be for example SiO 2 or Si 3 N ⁇ .
  • FIG. 2 shows the CrW thin film conductor 10 deposited on layer 12 after etching but before passivation and formation of the conformal Cr 2 Oj coating.
  • the thin film CrW conductor 14 is formed by depositing the CrW alloy layer 8 on a surface 12 of an integrated circuit and etching to form the desired pattern of interconnection line conductors 10 for the specific circuit.
  • the deposited CrW interconnection lines 10 are formed by etching in a manner well known in the integrated circuit art. After the CrW is deposited and lines 10 are etched on the integrated circuit surface they are heated in an appropriated atmosphere.
  • the chromium can be oxidized by heating the patterned CrW conductor lines 10 in hydrogen containing a small amount of water impurity. While this will oxidize the chromium to form the conformal layer 11, the same conditions will not oxidize the tungsten. Therefore, when the CrW film conductor 10 is heated in an appropriate hydrogen atmosphere some Cr diffuses to the surface and oxidizes.
  • the present invention is not specific to a particular CrW thin film composition but rather covers the basic use of Cr alloyed with W to provide an integrated circuit conductor for high temperature electronics that has: (a) Very low electromigration because of the W content; (b) Excellent adhesion to oxides, nitrides, etc because of the Cr content; (c)
  • the disclosed high temperature thin film integrated circuit metalization conductor 14 which utilizes a chromium tungsten alloy has better stability than prior art high temperature IC conductors.
  • One of its main improvements is an approximate 60% reduction in resistivity compared to the titanium tungsten thin film conductor while maintaining adequate step coverage.
  • the disclosed CrW thin film conductor 14 also has the benefit of not needing a deposited passivating coating or a special adhesion layer.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

A chromium/refractory metal alloy deposited thin film conductor (14) for use in high temperature semiconductor integrated circuit electronics suitable for operating temperatures as high as 400 °C. The thin film conductor (14) can be formed from a chromium tungsten alloy layer deposited on an integrated circuit surface (12). The chromium tungsten layer is then etched to form the desired conductor (10) pattern. The deposited chromium tungsten thin film conductor (10) is then heated in an atmosphere of hydrogen containing some water vapor, causing some of the chromium to diffuse to the surface and oxidize. This produces an excellent conformal passivating film (11) of Cr2O3. This also produces excellent adhesion to SiO2 and Si3N4. Further, the Cr enhances the surface mobility of sputter deposited refractory metal atoms yielding large, nonfibrous grains which enhance conformal step coverage and reduces electromigration.

Description

Chromium Refractory Metal Alloys Conductors For Use in High Temperature Integrated Circuits
Background of the Invention
1. Field of the Invention
This invention relates to high temperature electronics and more particularly to metal alloy conductors for use in high temperature semi¬ conductor integrated circuit electronics.
2. Description of Prior Art
Power integrated circuit electronics require high current densities (J) in parts of their thin film on - chip conductor networks. The mean time to failure (MTTF) due to electromigration in metal conductors used in integrated circuits varies as JN; where N is normally equal to or greater than two. The electromigration rate also increases exponentially with temperature. These two factors, current density and temperature, combine to make electromigration produced conductor opens (voids) or shorts (hillocks) major concerns as failure mechanisms in high temperature power integrated circuit electronics
Aluminum is clearly the present metal of choice for IC conductors. It provides low resistivity, resistance to corrosion, and with proper processing an excellent step coverage over non smooth surface morphology. However, the same basic property which permits good step coverage, tntra-atom bonds that are relatively easily broken, makes a material more susceptible to electromigration. While aluminum films are sufficiently stable to yield acceptable life in most power ICs at 125°C, there are serious life problems well below 200°C. Considerable effort has been expended to increase the high current density life of aluminum films through the addition of small percentages of other elements. Increases in life by over an order of magnitude have been reported with several different additions. However, the addition of other elements are also associated with increases in resistivity of the conductor.
Even if the increased resistivity is tolerable, a practical life for these alloys at power IC current densities have not been demonstrated for temperatures much above 200°C.
At the Second International High Temperature Electronics Conference two metalization schemes with conductors utilizing tungsten (W) for high 0 temperature electronics were reported on. The first was a patterned WN-W- WN sandwich with a passivating conformal silicon nitride (Si3N4) coating. This combination exhibited excellent stability even at 400°C and an acceptable resistivity. However, the growth pattern of sputter deposited W films creates a , _ fundamental problem with voids in step coverage. The reliability and life problems introduced by voids caused efforts to continue to find another conductor for high temperature integrated circuit applications.
The second metalization scheme used titanium tungsten (TiW) which was also passivated with a conformal SijN coating after patterning and which
20 was even more stable than the WN-W-WN conductor. This alloy, with 30 atomic percent Titanium, yields a much larger mobility for sputter deposited atoms. This eliminates the fibrous grain structure and produces much more conformal step coverage. However, the resistivity of TiW is greater than that 2 5 for W films by four times at 300°C and three times at 400°C.
While various conductors have been developed for high temperature operation, no clear choice has emerged. The need still remains for reliable interconnection line conductors and contacts with good step coverage,
30 acceptable resistivities, and low susceptibility to corrosion and electromigration for use in high temperature semiconductor integrated circuits.
Summary of the Invention
35 The present invention provides for improved conductors; for use in high temperature semiconductor integrated circuit electronics, which utilized chromium refractory metal alloys. The preferred combination for a high temperature thin film conductor with desirable properties are alloys of tungsten (W) with chromium (Cr). The tungsten chromium combination is deposited and etched to form the desired interconnections and contacts on an integrated circuit. When the deposited CrW thin film conductor is heated in an appropriate atmosphere some chromium diffuses to the surface and oxidizes.
This produces an excellent conformal passivating film of Cr2O3 To a major degree fractures of the Cr2O3 are self healing by the same mechanism. The Cr also provides adhesion and improves the structure of sputter deposited films
These factors combine to give CrW the longest MTF in a high temperature oxidizing environment of any thin film conductor evaluated for IC applications.
These advantages can be achieved with films containing approximately 10 atomic percent chromium and 90 atomic percent tungsten.
Brief Description of the Drawings
For a better understanding of the invention reference may be had to the preferred embodiment exemplary of the invention shown in the accompanying drawings in which: FIG. 1 is a section view of a CrW thin film conductor according to the present invention;
FIG. 2 is a section view, similar to FIG. 1, taken in Fig. 3 along the line II - π prior to passivation;
FIG. 3 is a perspective view of a portion of an integrated circuit showing some exemplary interconnect line conductors; and,
FIG. 4 shows a CrW alloy deposited on an integrated circuit surface prior to etching to form the patterned interconnections lines.
Detailed Description of the Preferred Embodiments
Refer now to the drawings and FIG. 1 in particular there is shown a cross section of a thin film CrW conductor 14 according to the present invention, suitable for use in high temperature semiconductor integrated circuit electronics. The thin file conductor 14 is formed by depositing a CrW alloy layer 8, as shown in FIG. 4, on a layer 12 which will form part of an integrated circuit. The thin -4- film passivated CrW conductor 14 can be formed by depositing on layer 12 the thin film CrW layer 8 by means well known in the art such as sputtering, simultaneous E-beam vacuum evaporation, or the like. The CrW alloy layer 8 is then etched to form the desired pattern of interconnection lines 10 as shown in FIG. 3. The layer on which conductor 14 is formed can be for example SiO2 or Si3N<. FIG. 2 shows the CrW thin film conductor 10 deposited on layer 12 after etching but before passivation and formation of the conformal Cr2Oj coating.
Two major effects that limit the life of thin film conductors at high temperatures are electromigration (EM) and corrosion. Because of its high melting temperature, W is probably the most EM resistant metal there is, but its corrosion resistance is very poor. Metalization schemes which incoφorated W (to benefit from its high EM resistance) with other materials (which provide passivation and adhesion) have been evaluated by the inventors. The best combination found for a high temperature thin film conductor with several desirable properties, has been alloys of W with Cr.
The thin film CrW conductor 14 is formed by depositing the CrW alloy layer 8 on a surface 12 of an integrated circuit and etching to form the desired pattern of interconnection line conductors 10 for the specific circuit. The deposited CrW interconnection lines 10 are formed by etching in a manner well known in the integrated circuit art. After the CrW is deposited and lines 10 are etched on the integrated circuit surface they are heated in an appropriated atmosphere. In practicing the invention the chromium can be oxidized by heating the patterned CrW conductor lines 10 in hydrogen containing a small amount of water impurity. While this will oxidize the chromium to form the conformal layer 11, the same conditions will not oxidize the tungsten. Therefore, when the CrW film conductor 10 is heated in an appropriate hydrogen atmosphere some Cr diffuses to the surface and oxidizes.
When the unpassivated CrW thin film conductor, shown in FIG. 2, is heated in the hydrogen atmosphere some Cr diffuses to the surface and oxidizes forming a thin coating. This produces an excellent conformal passivating film of Cr2U3. A Cr depleted region 13 is formed beneath the conformal Cr2O3 coating 11. The passivation properties of Cr2O3 in stainless steels are well established. This includes the self healing of fractures in the Cr2O3 as described above. The Cr also provides strong adhesion of the CrW to oxide, nitride, and other surfaces Another benefit of Cr is that its presence markedly increases the surface mobility of the W atoms on a film being produced by vacuum deposition. This results in deposited films with much better conformity, larger grains and less fibrous structure then that typical of vacuum deposited pure W films. This is particularly important in multilevel metal applications.
Shadowing by fibrous (columnar) grains growing from, non-horizontal surfaces leads to voids, in concave corners of both contacts and vias, between metal layers Also, columnar growth on convex corners produces wide grain boundaries which are excessively susceptible to chemical attack, also resulting in voids.
Unfortunately, there are some disadvantages to the presence of Cr in a W film. An important one is related to the passivation the Cr produces Etching of the W becomes increasingly more difficult as the Cr content increases. Also, as with all metal alloys the resistivity increases with increasing Cr content. The benefits of Cr in passivation, adhesion, and grain structure, of course, decrease with decreased Cr content. Consequently, some compromise between properties must be made in developing a preferred composition. Since a number of conditions in the deposition system (e.g. sputtering system geometry, substrate temperature, impurity partial pressure, substrate bias, etc ) also influence film properties such as resistivity, stress, and step coverage, there is not one optimum CrW composition. The present invention is not specific to a particular CrW thin film composition but rather covers the basic use of Cr alloyed with W to provide an integrated circuit conductor for high temperature electronics that has: (a) Very low electromigration because of the W content; (b) Excellent adhesion to oxides, nitrides, etc because of the Cr content; (c)
Excellent self passivation provided by the conformal Cr2O3 coating; and (d) Conformity and grain structure much improved over that typical of vacuum deposited W films. We have demonstrated that these advantages can be achieved with films containing 10 atomic percent Cr and 90 atomic percent W. With this composition a 300°C resistivity of less than 24 μΩ cm can be obtained. This is less than 3.8 times Al film resistivity at 300°C. This is sufficiently low for a host of high temperature applications. Life tests on self passivated conductor films of the 10% Cr - 90% W alloy extrapolate to a life (Δ R/R < 0.1) of over 8 years with current densities of 106A/cm2 at a temperature of 300°C.
Because EM varies exponentially with temperature, somewhat below 400°C there are other refractory metals which can be combined with Cr to achieve benefits similar to those of CrW. In some cases an improvement over CrW can be achieved in one or more of the important properties of the conducting film. For example, substituting Mo for W results in films which are more easily etched and demonstrate better step coverage. Substituting Rh for W yields reduced resistivity. Therefore, the techniques of this invention also apply to all Cr - refractory metal combinations for which the melting point is high enough to correspond to insignificant electromigration at the required operating conditions.
The disclosed high temperature thin film integrated circuit metalization conductor 14 which utilizes a chromium tungsten alloy has better stability than prior art high temperature IC conductors. One of its main improvements is an approximate 60% reduction in resistivity compared to the titanium tungsten thin film conductor while maintaining adequate step coverage. The disclosed CrW thin film conductor 14 also has the benefit of not needing a deposited passivating coating or a special adhesion layer.

Claims

Oaims:
1. A improved thin film conductor for use on high temperature electronics integrated circuit boards comprising: a thin film conductor formed from chromium and a refractory metal; and, a passivating film of Cr2O3 formed on the surface of said thin film conductor.
2. A thin film conductor as claimed in Claim 1 wherein the thin film conductor contains approximately 10% chromium and 90% tungsten.
3. A method of forming a thin film conductor on a high temperature integrated circuit comprising the steps of: a) forming a chromium tungsten alloy on the integrated circuit to define the thin film conductor pattern; and, b) heating the formed thin film conductor in an atmosphere containing some moisture to produce a conformal passivating film of Cr2O3 on the surface of the thin film conductor.
4. A method as claimed in Claim 3 wherein the thin film conductor pattern is formed by depositing a chromium tungsten alloy layer on the integrated circuit and etching the deposited layer to form the thin film conductor pattern.
5. A method as claimed in Claim 3 wherein the atmosphere in which the formed thin film conductor is heated comprises hydrogen and a small amount of water.
6. A high temperature integrated circuit interconnection structure comprising: a substrata formed on the integrated circuit wafer; and, thin film conductors formed on said substrata from an alloy containing chromium and a refractory metal having a melting point high enough to correspond to insignificant electromigration at the required integrated circuit operating temperature.
7. A device as claimed in Claim 6 wherein the refractory metal is selected from the group comprising Mo, W and Rh.
8. A device as claimed in Claim 7 wherein a Cr2O3 passivating film is formed on the surface of the thin film conductor.
PCT/US1997/002278 1996-02-16 1997-02-12 Chromium refractory metal alloys conductors for use in high temperature integrated circuits WO1997030476A1 (en)

Applications Claiming Priority (2)

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US60267196A 1996-02-16 1996-02-16
US08/602,671 1996-02-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3939293A (en) * 1974-04-30 1976-02-17 International Business Machines, Corporation Method for passivating chromium
US4231058A (en) * 1978-11-22 1980-10-28 The United States Of America As Represented By The Secretary Of The Navy Tungsten-titanium-chromium/gold semiconductor metallization
JPS62145870A (en) * 1985-12-20 1987-06-29 Matsushita Electric Ind Co Ltd Thin film transistor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3939293A (en) * 1974-04-30 1976-02-17 International Business Machines, Corporation Method for passivating chromium
US4231058A (en) * 1978-11-22 1980-10-28 The United States Of America As Represented By The Secretary Of The Navy Tungsten-titanium-chromium/gold semiconductor metallization
JPS62145870A (en) * 1985-12-20 1987-06-29 Matsushita Electric Ind Co Ltd Thin film transistor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M. J. KIM, R. A. SAIA, B. GOROWITZ: "Mo/Cr Metallization for Silicon Device Interconnection", J. ELECTROCHEM.SOC., vol. 134, no. 6, June 1987 (1987-06-01), pages 1554 - 1558, XP002031314 *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 382 (E - 564) 12 December 1987 (1987-12-12) *

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