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GB2204065A - Vapour deposited metal films for integrated circuit manufacture - Google Patents

Vapour deposited metal films for integrated circuit manufacture Download PDF

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Publication number
GB2204065A
GB2204065A GB08702999A GB8702999A GB2204065A GB 2204065 A GB2204065 A GB 2204065A GB 08702999 A GB08702999 A GB 08702999A GB 8702999 A GB8702999 A GB 8702999A GB 2204065 A GB2204065 A GB 2204065A
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United Kingdom
Prior art keywords
metal
layer
deposited
metal film
pseudoamorphous
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
GB08702999A
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GB8702999D0 (en
Inventor
Paul Gideon Huggett
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GE Healthcare UK Ltd
Plessey Co Ltd
Original Assignee
GE Healthcare UK Ltd
Plessey Co Ltd
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 GE Healthcare UK Ltd, Plessey Co Ltd filed Critical GE Healthcare UK Ltd
Priority to GB08702999A priority Critical patent/GB2204065A/en
Publication of GB8702999D0 publication Critical patent/GB8702999D0/en
Publication of GB2204065A publication Critical patent/GB2204065A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/52Controlling or regulating the coating process
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical 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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

A process for forming a vapour deposited metal film of tungsten or molybdenum, the process comprising the steps of providing a substrate surface capable of supporting the required film, heating the substrate surface in a vapour deposition chamber, admitting a decomposable compound of the selected metal in vapour form to said chamber, decomposing said compound such that a film of the metal is deposited on said surface, interrupting said decomposition step when a predetermined thickness of said metal film has been formed, depositing a pseudoamorphous layer of the metal effective to provide new crystal nucleation centres on the previously deposited metal film, continuing the metal deposition until a further predetermined metal film thickness has been formed, interrupting the deposition process and removing the required substrate with metal film from said chamber. The pseudoamorphous layer may be produced by 1) deposition of silicon from a silicon-containing gas and contact with the metal compound vapour to replace the silicon layer with new metal deposition nuclei or 2) deposition from the metal carbonyl. Improves the surface roughness. <IMAGE>

Description

VAPOUR DEPQS1TED METAL FILMS This invention relates to vapour deposited metal films. It relates particularly to films which are deposited by a chemical process and where the metals include tungsten and molybdenum.
In the construction of integrated circuit devices such as Very Large Scale Integrated circuits it is necessary for a body of a substrate material to be given an electrically conductive coating.
Where the electrically conductive coating is to be formed of tungsten, it has been found that a low pressure chemical vapour deposition process using tungsten hexafluoride in the presence of hydrogen as a gaseous reducing agent is, in general, a satisfactory process to use. This process, however, can give significant surface roughness in the deposited film. This is due to the growth of preferred crystallographic facets which cause certain crystal planes to protrude above the average film thickness. Typically, a film one micrometre (1,000 nanometres) in thickness grown by this technique will have an average surface roughness of plus or minus 150 nanometres. Roughness of this order will cause a problem when the film is intended to be further processed for use as a conducting material in integrated circuit device construction.In particular, if the film is to be etched by an anisotropic process, the presence of the roughness dictates that a large overetch must be employed in order to clear etched areas thus exposing the lower layers to the etchant material and possibly causing serious damage. Also the effectiveness of optical lithographic techniques commonly used in integrated circuit processing can be severely compromised by the presence of rough, highly reflective metal surfaces.
The presence of a rough metal surface can also have electrical property implications since a severely rough metal surface will cause a degradation in the dielectric quality of an electrical insulation layer which is subsequently deposited on the metal surface.
An object of the present invention therefore is to improve the surface smoothness of vapour deposited tungsten and molybdenum films.
According to the invention, there is provided a process for forming a vapour deposited metal film of tungsten or molybdenum, the process comprising the steps of providing a substrate surface capable of supporting the required film, heating the substrate surface in a vapour deposition chamber, admitting a decomposable compound of the selected metal in vapour form to said chamber, decomposing said compound such that a film of the metal is deposited on said surface, interrupting said decomposition step when a predetermined thickness of said metal film has been formed, depositing a pseudoamorphous layer of the metal effective to provide new crystal nucleation centres on the previously deposited metal film, continuing the metal deposition until a further predetermined metal film thickness has been formed, interrupting the deposition process and removing the required substrate with metal film from said chamber.
Preferably, the pseudoamorphous layer is deposited by the steps of admitting a flow of a silicon containing gas to said chamber and decomposing said gas such that a silicon layer is deposited on said metal film, replacing said gas flow with the metal compound vapour such that the freshly deposited silicon layer is replaced with the metal thus forming new metal deposition nuclei on the previously deposited metal film.
In an alternative embodiment, the pseudoamorphous layer is deposited by the steps of admitting a flow of a carbonyl compound of the metal and decomposing this to form the pseudoamorphous layer.
In a further embodiment, the pseudoamorphous layer is deposited by the step of initiating a radiofrequency electrical discharge within the decomposable metal vapour compound atmosphere or within an atmosphere of a silicon containing gas in the chamber.
The step of depositing the pseudoamorphous layer before a further metal film layer may be repeated one or more times. The step of depositing the pseudoamorphous layer may be effected at the same temperature as that required to deposit the metal film.
The silicon containing gas may be silane or a polysilane such as disilane.
Conveniently, the deposition step is effected at a temperature of less than 5000 C, such as one between 400 and 425or.
Promotion of the pseudoamorphous layer deposition stage may be effected by radiofrequency electrical discharge means in the deposition chamber.
A particular embodiment of the present invention will now be described, by way of example, with reference to the accompanying drawing, in which; Figure 1 is a cross-sectional view greatly enlarged showing a body of substrate material carrying a vapour deposited tungsten film, Figure 2 is a similar view showing a film which has been treated to give a renucleated tungsten surface of greater smoothness, and, Figure 3 is a schematic diagram of a tungsten-deposition apparatus for low pressure chemical vapour deposition.
The problem of the increased surface roughening that can occur with a chemical vapour deposit of tungsten can be seen in the crosssectional view of Figure 1. This Figure shows a silicon wafer substrate 1 which has been given a low pressure chemical vapour deposition coating 2 of tungsten in a single deposition stage of one hour duration. Initially, the upper surface of the substrate 1 is seen to be smooth but the body of tungsten as it is laid down on the substrate surface commences as a crystalline growth from a number of nucleation points. Different planes of the resulting crystals grow forward at different rates so that the initially smooth upper surface of the combination becomes increasingly more roughened as certain planes protrude above the average film thickness.
As depicted in the Figure, when the coating 2 has a thickness of about one micrometre the average surface roughness can be about 150 nanometres.
The process of the present invention in one embodiment makes use of a chemically deposited layer of silicon which is laid down on top of the tungsten coating 2. After this step, the further deposition of tungsten from the tungsten hexafluoride vapour will result in the silicon film chemically reducing the vapour to produce a pseudoamorphous tungsten deposit which thus has no particular tendency to promote crystal plane growth.
The silicon lying on the previously deposited tungsten surface will be spontaneously removed by the reduction process so that the coating 2 includes only the tungsten metal deposit that is required.
The pseudoamorphous tungsten deposit provides a suitable base for the further growth of tungsten since a surface that is capable of uniform growth has now been recreated.
Figure 2 shows a similar substrate 1 which has supported four tungsten deposition stages with intervening silicon deposition stages.
The total tungsten deposition time as with the embodiment of Figure 1 was one hour and the upper tungsten surface 3 is now seen to be very much smoother than that of Figure 1. After each silicon deposition stage, the pseudoamorphous tungsten growth which formed allowed new crystal growth to start from the upper surface and the crystals, at least initially, will be small so that the occurrence of fast growing crystal planes will be minimised. With further deposition of the tungsten film, the crystal planes will again resume their irregular growth pattern and the formation of a rough surface is again a possibility. The step of interrupting the tungsten deposition and laying down a temporary silicon deposit may thus be repeated as often as necessary until the required final thickness of the tungsten deposit has been achieved.
It will be noted that an initial film of tungsten is grown to the predetermined thickness by the reaction between tungsten hexafluoride (WF6) and hydrogen. A film of amorphous silicon is then deposited at the same temperature by the pyrolysis of disilane.
The tungsten deposition is then continued, the silicon being consumed by the reaction: 2WF6(g) + 3 Si(s) 3 Si F4(g) + 2W(s) The thickness and uniformity of the silicon layer has been found not to be too critical provided that (a) sufficient tungsten is deposited by the chemical reaction just described in order to completely recreate a uniformly grossing surface, and (b) the silicon thickness is sufficiently thin to be totally consumed in this reaction. This implies a silicon thickness of 2-20 nanometres. Thus, the process is highly tolerant of poor uniformity control. The number of renucleation steps necessary is dependent on the final thickness required for the tungsten film and the required smoothness.In practice, it has been found sufficient to renucleate the surface every 250 nanometres thickness of tungsten grown in order to significantly improve the smoothness.
Figure 3 shows the tungsten deposition apparatus used for the experimental work. In this Figure, a horizontally disposed vapour deposition chamber 6 is depicted having a loading door assembly 7 and which is capable of being heated by resistance heater elements 8 under the control of a temperature controller 9. The deposition chamber 6 also includes a gas pressure sensor 11.
A gas flow supply for the deposition chamber 6 is provided through reactive gas lines 12 which are connected through a gas control system 13 to a tungsten hexafluoride (WF6) supply source 14.
Also provided is a disilane supply source 15. The control system 13 also controls supplies of argon from an argon source 16 and hydrogen from a hydrogen source 17. The hydrogen gas supply is delivered through a palladium diffuser 18 which serves to improve the purity of the hydrogen as it is delivered to the chamber 6.
A gas outlet from the deposition chamber 6 is connected through a vibration absorbing flexible hose 19 to a Roots blower 21 which is backed by a vacuum pump 22. A vacuum valve 23 is also provided.
In one example of use of the deposition apparatus, silicon wafers are cleaned by standard cleaning procedures and a layer approximately 100 nanometres in thickness of silicon dioxide is grown on the surface by thermal oxidation. An adhesion layer of titanium having a thickness of 100 nanometres is then applied by a DC sputtering process. The resulting wafer bodies are then loaded into the deposition chamber 6 and heated to 4400C in a hydrogen gas ambient atmosphere at 400mTorr for thirty minutes.A tungsten film is then deposited by admitting a flow of 100 standard cubic centimetres per minute (sccm) of tungsten hexafluoride and one standard litre per minute (slm) of hydrogen at a pressure of 400mTorr and a temperature of 4400 C. This step is continued for twelve minutes after which the flow of gases is interrupted and the system is allowed to reach base pressure for one minute. Disilane - in a mixture with argon is then admitted at 50 sccm and a pressure of SOOmTorr at the same temperature for a period of ten minutes. The flow of gases is then interrupted again and the system is allowed to reach base pressure for one minute. Further tungsten is then deposited using the conditions already described.
A total of four tungsten growth steps and three disilane growth steps are employed. The total thickness of the resulting tungsten film is 0.8 micrometres. The surface roughness was estimated from electron micrographs to be approximately 50 nanometres This value can be compared with that for a tungsten film deposited without the additional disilane steps for the same length of time. In this case, the film thickness was identical but the surface roughness was about 200 nanometres. There was no difference able to be measured in the electrical sheet resistance of the two differently produced types of film.
In a second example of use of the deposition apparatus, silicon wafers are prepared as before. They are heated to 4000C in a hydrogen gas ambient atmosphere at 450mTorr for one hour in a graphite plasma deposition boat of a design commonly used in the semiconductor industry. Tungsten is then deposited by conditions identical to those of the first example. After fifteen minutes, the flow of gases is interrupted and 200 sccm of silane (SiH < ) and 200 sccm of argon are admitted to the chamber at SOOmTorr. A radiofrequency electrical discharge is then applied through an electrode (not shown) which is located in the chamber 6. The electrical energy was supplied by means of a power supply generator (Advanced Energy Systems) providing one kilowatt of power for ten minutes.The silane supply is then removed and the tungsten deposition resumed.
A total of four tungsten growth steps and three silane growth steps yielded a tungsten film of 0.8 micrometre in thickness with a surface roughness of about 50 nanometres A control growth operation carried out without the silane plasma steps produced a surface roughness of about 200 nanometres.
The foregoing descriptions of embodiments of the invention have been given by way of example only and a number of modifications may be made without departing from the scope of the invention as defined in the appended claims. For instance, it is not essential that the metal film to be deposited should be tungsten and in an alternative embodiment the metal could, for example, be molybdenum. It may also be possible to deposit the pseudoamorphous layer by alternative means, for example from the metal carbonyl, that is M(CO)6, where M = W or Mo, or alternatively by a radiofrequency discharge of the metal hexafluoride in hydrogen.

Claims (11)

1. A process for forming a vapour deposited metal film of tungsten or molybdenum, the process comprising the steps of providing a substrate surface capable of supporting the required film, heating the substrate surface in a vapour deposition chamber, admitting a decomposable compound of the selected metal in vapour form to said chamber, decomposing said compound such that a film of the metal is deposited on said surface, interrupting said decomposition step when a predetermined thickness of said metal film has been formed, depositing a pseudoamorphous layer of the metal effective to provide new crystal nucleation centres on the previously deposited metal film, continuing the metal deposition until a further predetermined metal film thickness has been formed, interrupting the deposition process and removing the required substrate with metal film from said chamber.
2. A processs as claimed in Claim 1, in which the pseudoamorphous layer is deposited by the steps of admitting a flow of a silicon containing gas to said chamber and decomposing said gas such that a silicon layer is deposited on said metal film, replacing said gas flow with the metal compound vapour such that the freshly deposited silicon layer is replaced with the metal thus forming new metal deposition nuclei on the previously deposited metal film.
3. A process as claimed in Claim 1, in which the pseudoamorphous layer is deposited by the steps of admitting a flow of a carbonyl compound of the metal and decomposing this to form the pseudoamorphous layer.
4. A process as claimed in Claim 1, in which the pseudoamorphous layer is deposited by the step of initiating a radiofrequency electrical discharge within the decomposable metal vapour compound atmosphere or within an atmosphere of a silicon containing gas in the chamber.
5. A process as claimed in any one of Claims 1 to 4, in which the step of depositing said pseudoamorphous layer before a further metal film layer is repeated one or more times.
6. A process as claimed in any one of Claims 1 to 5, in which the step of depositing said pseudoamorphous layer is effected at the same temperature as that required to deposit the said metal film.
7. A process as claimed in Claim 2, in which the silicon containing gas is silane or a polysilane such as disilane.
8. A process as claimed in any one of Claims 1 to 7, in which the deposition step is effected at a temperature of less than 5000 C, such as one between 400 and 4250 C.
9. A process as claimed in any one of Claims 1 to 3 or 5 to 8, in which promotion of the pseudoamorphous layer deposition stage is effected by radiofrequency electrical discharge means in said chamber.
10. A process for forming a vapour deposited metal film of tungsten or molybdenum, substantially as hereinbefore described with reference to the accompanying drawing.
11. A vapour deposited metal film of tungsten or molybdenum, when formed by a process as claimed in any one of Claims 1 to 10.
11. A vapour deposited metal film of tungsten or molybdenum, when formed by a process as claimed in any one of Claims 1 to 10.
Amendments to the claims have been filed as follows CLAIMS 1. A process for forming a vapour deposited metal film of high purity tungsten or molybdenum, the process comprising the steps of providing a substrate surface capable of supporting the required film, heating the substrate surface in a low pressure chemical vapour deposition chamber, admitting a decomposable compound of the selected metal in vapour form to said chamber, decomposing said compound such that a film of the metal is deposited on said surface, interrupting said decomposition step when a predetermined thickness of said metal film has been formed, depositing a p eudoamorphous layer of the metal effective to provide new crystal nucleation centres on the previously deposited metal film, continuing the metal deposition until a further predetermined metal film thickness has been formed, interrupting the deposition process and removing the required substrate with metal film from said chamber.
2. A process as claimed in Claim 1, in which the pseudoamorphous layer is deposited by the steps of admitting a flow of a silicon containing gas to said chamber and decomposing said gas such that a continuous silicon layer is deposited on said metal film, replacing said gas flow with the metal compound vapour such that the freshly deposited silicon layer is replaced with the metal thus forming new metal deposition nuclei on the previously deposited metal film.
3. A process as claimed in Claim 1, in which the pseudoamorphous layer is deposited by the steps of admitting a flow of a carbonyl compound of the metal and decomposing this to form the pseudoamorphous layer.
4. A process as claimed in Claim 1, in which the pseudoamorphous layer is deposited by the step of initiating a radiofrequency electrical discharge within the decomposable metal vapour compound atmosphere or within an atmosphere of a silicon containing gas in the chamber.
5. A process as claimed in any one of Claims 1 to 4, in which the step of depositing said pseudoamorphous layer before a further metal film layer is repeated one or more times.
6. A process as claimed in any one of Claims 1 to 5, in which the step of depositing said pseudoamorphous layer is effected at the same temperature as that required to deposit the said metal film.
7. A process as claimed in Claim 2, in which the silicon containing gas is silane or a polysilane such as disilane.
8. A process as claimed in any one of Claims 1 to 7, in which the deposition step is effected at a temperature of less than 5000 C, such as one between 400 and 4250C..
9. A process as claimed in any one of Claims 1 to 3 or 5 to 8, in which promotion of the pseudoamorphous layer deposition stage is effected by radiofrequency electrical discharge means in said chamber.
10. A process for forming a vapour deposited metal film of tungsten or molybdenum, substantially as hereinbefore described with reference to the accompanying drawing.
GB08702999A 1987-02-10 1987-02-10 Vapour deposited metal films for integrated circuit manufacture Pending GB2204065A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB08702999A GB2204065A (en) 1987-02-10 1987-02-10 Vapour deposited metal films for integrated circuit manufacture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB08702999A GB2204065A (en) 1987-02-10 1987-02-10 Vapour deposited metal films for integrated circuit manufacture

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GB8702999D0 GB8702999D0 (en) 1987-03-18
GB2204065A true GB2204065A (en) 1988-11-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230142966A1 (en) * 2021-11-10 2023-05-11 Entegris, Inc. Molybdenum precursor compounds

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1186892A (en) * 1966-04-16 1970-04-08 Philips Electronic Associated Improvements in and relating to Methods of Providing Polycrystalline Layers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1186892A (en) * 1966-04-16 1970-04-08 Philips Electronic Associated Improvements in and relating to Methods of Providing Polycrystalline Layers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230142966A1 (en) * 2021-11-10 2023-05-11 Entegris, Inc. Molybdenum precursor compounds
US12297531B2 (en) * 2021-11-10 2025-05-13 Entegris, Inc. Methods of preparing molybdenum-containing films

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