Process for deposition of a tungsten layer on a semiconductor wafer

Abstract: An process is disclosed for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvements comprise depositing tungsten on the semiconductor wafer in the presence of nitrogen gas to improve the reflec­ tivity of the surface of the resulting layer of tungsten; maintaining the vacuum chamber at a pressure of from about 20 to 760 Torr to improve the deposition rate of the tungsten, as well as to improve the reflectivity of the tungsten surface; and, when needed, the additional step of forming a nucleation layer on the semiconductor layer prior to the step of depositing tungsten on the semicon­ ductor wafer to improve the uniformity of the depo­ sited tungsten layer.

Description: 1. Field of the Invention This invention relates to the processing of semiconductor wafers. More particularly, this invention relates to improvements in the process of depositing a tungsten layer on a semiconductor wafer. 2. Description of the Related Art In the formation of integrated circuit structures on and in a semiconductor wafer such as a silicon wafer, one or more metals layers are conventionally used to form conductive interconnects or wiring harnesses to various contacts on the processed wafer. Such metal wiring harnesses or patterned metal layers have, in the past, utilized either aluminum or gold as the metal. From an economical standpoint, aluminum is preferred to gold. However, as the geometries of the integrated circuit structures become smaller and smaller, the use of tungsten metal, instead of aluminum, has become preferred due to the better step coverage and filling of small contact holes or vias by CVD tungsten. However, the blanket deposition of a layer of tungsten on a semiconductor wafer is not without problems. First of all, the conventional deposition of tungsten at about 350°C is rather slow, i.e., about 30 nm (300 Å) per minute. Higher rates, e.g., about 100 nm (1000 Å) per minute, are achievable, but only by raising the temperature up to about 500-550°C, which may risk damage to underlying portions of the integrated circuit structure. Furthermore, the resulting layer of tungsten is not always smooth, resulting in a reflectivity which may be only 20% or less that of a silicon surface, making subsequent patterning of the tungsten layer by photolithography techniques more difficult. Also, the uniformity of the deposition may vary over 1% in thickness across the wafer, as measured by the resistivity. For example, document EXT. ABS. 20th INT. CONF. ON SOLID STATE DEVICES AND MATERIALS, TOKYO, 24-26/8/1988, IEEE JAPAN, P 85-88, N. KOBAYASHI ET AL "TUNGSTEN PLUG TECHNOLOGY: SUBSTITUTING W FOR Si USING WF6" relates to CVD deposition of tungsten in a reaction chamber. Reactants include WF 6 IN 2 . Furthermore Document JOURNAL OF VACUUM SCIENCE AND TECHNOLOGY: PART B; Vol. 4, No. 5, October 1986, New York U.S.A., pages 1175 to 1179; Y. Shioya et al: "BARRIER EFFECT OF SELECTIVE CHEMICAL VAPOUR DEPOSITED TUNGSTEN FILMS" relates to CVD deposition of tungsten in a reaction chamber. Reactants include WF 6 IN 2 IH 2 . Both mentioned processes suffer from the above mentioned disadvantages. It would, therefore, be beneficial to provide improvements in the process for the blanket deposition of a tungsten layer on a semiconductor wafer wherein the deposition rate could be accelerated and the reflectivity of the resulting tungsten layer improved, as well as providing a more uniform layer. The present invention therefore provides improved processes according to independent claim 1. Further advantageous features of the processes are evident from the dependent claims, the description and the enclosed figure. It is, therefore, an aspect of this invention to provide an improved process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvement comprises depositing tungsten on a semiconductor wafer in the presence of nitrogen gas to improve the reflectivity of the resulting layer of tungsten at a pressure of from about 2.66 kPa to 101.3 kPa (20 to 760 Torr) to improve the tungsten deposition rate, as well as to improve the reflectivity of the surface of the tungsten layer. It is yet another aspect of this invention that the process additionally comprises the step of forming a nucleation layer on the semiconductor layer prior to the step of depositing tungsten on the semiconductor wafer to improve the uniformity of the deposited layer of tungsten. It is still another aspect of this invention to provide an improved process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvements comprise the additional step of forming a nucleation layer on the semiconductor layer prior to the step of depositing tungsten on the semiconductor wafer to improve the uniformity of the deposited tungsten layer; and then depositing tungsten over the nucleation layer on the semiconductor wafer preferably at a pressure of from about 2.66kPa to 101.3kPa (about 20 to about 760 Torr) in the presence of nitrogen gas to improve the reflectivity of the resulting layer of tungsten. It is a further aspect of this invention to provide an improved process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvements comprise the step of forming a nucleation layer on the semiconductor layer prior to the step of depositing tungsten on the semiconductor wafer to improve the uniformity of the deposited tungsten layer; and then depositing tungsten over the nucleation layer on the semi-conductor wafer at a pressure of from about 2.66kPa to 101.3kPa (about 20 to 760 Torr) to improve the tungsten deposition rate, as well as to improve the reflectivity of the surface of the tungsten layer. It is yet a further aspect of this invention to provide an improved process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvements comprise depositing tungsten on the semiconductor wafer in the presence of nitrogen gas and at a pressure of from about 2.66kPa to 101.3kPa (about 20 to 760 Torr) to improve the reflectivity of the surface of the resulting tungsten layer, as well as to improve the tungsten deposition rate. It is still a further aspect of this invention to provide an improved process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvements comprise the additional step of forming a nucleation layer on the semiconductor layer prior to the step of depositing tungsten on the semiconductor wafer to improve the uniformity of the deposited tungsten layer; and then depositing tungsten over the nucleation layer on the semiconductor wafer in the presence of nitrogen gas and at a pressure of from about 2.66kPa to 101.3kPa (about 20 to 760 Torr) to improve the reflectivity of the surface of the resulting tungsten layer, as well as to improve the tungsten disposition rate. Finally, it is still a further aspect of this invention to provide a process according to the aforementioned aspects in which the nucleation layer is provided over a previously formed layer of titanium nitride to improve the uniformity of the deposited tungsten layer or in which the tungsten layer is formed over a previously formed layer on said semi-conductor wafer selected from the class consisting of a tungsten, a titanium tungsten and a titanium nitrite layer. According to an especially preferred aspect, the invention provides an improved process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber wherein the improvement comprises: (a) forming a nucleation layer on a semiconductor wafer prior to the step of depositing tungsten on the semiconductor wafer by contacting said wafer with a mixture of gases flowing through said vacuum chamber to form said nucleation layer comprising: (i) from 5 to about 50 sccm WF 6 ; (ii) from about 500 to about 3000 sccm Ar; (iii) from about 20 to about 300 sccm N 2 , and (iv) from about 5 to about 50 sccm SiH 4 ; and (b) then depositing tungsten on said semiconductor wafer over said nucleation layer by contacting said wafer with a mixture of gases flowing through said vacuum chamber comprising: (i) from about 20 to about 200 sccm WF 6 ; (ii) from about 100 to about 5000 sccm Ar; (iii) from about 10 to about 300 sccm N 2 , and (iv) from about 300 to about 3000 sccm H 2 ; while maintaining the pressure in said vacuum chamber at from about 10kPa (about 75 Torr) to about 11.3kPa (about 85 Torr) and the susceptor temperature at from about 450°C to about 475°C during said tungsten deposition step. The process is preferably carried out as a chemical vacuum deposition (CVD) process The above aspects and further objects of the invention will be apparent from the following description, as well as the accompanying flowwsheet in the single figure illustrating the process of the invention. The invention provides improvements in the process for forming a layer of tungsten over a semiconductor wafer whereby the reflectivity of the surface of the tungsten layer may be improved, and the rate of deposition of the tungsten layer may be increased as well. In one embodiment, the reflectivity of the surface of the tungsten layer may be improved by the presence of nitrogen gas during the deposition. The deposition rate may also be improved by increasing the pressure during the deposition, which will also have a beneficial effect on the reflectivity of the surface of the resulting tungsten layer. Furthermore, in another embodiment, the process also includes improving the uniformity of the coating layer by forming a nucleation layer on the wafer prior to forming the tungsten layer. In the practice of the process of the invention, a semiconductor wafer is utilized such as a silicon substrate which may have portions of an integrated circuit structure already formed therein, such as, for example, one or more transistors. An insulating layer, such as a silicon oxide layer, which has been previously patterned to provide openings or vias to underlying portions of the integrated circuit structure formed in the silicon substrate will usually have been formed over the underlying silicon substrate and the integrated circuit structures formed therein. An intermediate layer is formed over the insulating layer to facilitate adherence of the tungsten layer to the underlying structure, since a layer of tungsten cannot be applied by chemical vapor deposition (CVD) directly to a silicon oxide layer. The intermediate layer may comprise any material which is chemically compatible with both the underlying insulating layer and the tungsten layer which will be applied thereon, including good adhesion to both the tungsten and insulating layers. Examples of materials which may comprise the intermediate layer include sputtered tungsten, sputtered titanium tungsten (TiW), or titanium nitride (TiN), which may be applied by sputtering of TiN, reactive sputtering of a titanium target in the presence of nitrogen, sputtering of titanium followed by thermal reaction with nitrogen, or by CVD deposition of TiN. In accordance with one embodiment of the invention, a tungsten layer is deposited directly over the intermediate layer by CVD deposition using a combination of WF 6 , Ar, N 2 , and H 2 gases in a vacuum chamber. The gaseous mixture is flowed into the vacuum deposition chamber at a rate of from about 20 to about 200 standard cubic centimeters per minute (sccm) of WF 6 , preferably from about 20 to about 100 sccm; from about 100 to about 5000 sccm of an inert carrier gas such as argon, preferably about 1000 to about 3000 sccm; from about 10 to about 300 sccm of nitrogen; and from about 300 to about 2000 sccm of hydrogen, preferably about 500 to about 2000 sccm. The presence of nitrogen in the mixture of gases used in the tungsten deposition, in accordance with the invention, has been found to increase the reflectivity of the deposited tungsten layer which facilitates the use of photolithography in a subsequent patterning step. The reflectivity of the tungsten layer is measured as a comparison to the reflectivity of a silicon layer, with 100% indicating a reflectivity equal to that of a silicon surface. During the tungsten CVD deposition, the pressure in the vacuum chamber is maintained at from about 2.66kPa to about 101.3KPa (about 20 to about 760 Torr), preferably from about 7.99kPa to about 13.33kPa (about 60 to about 100 Torr), and most preferably from about 10kPa to about 11.3kPa (about 75 to about 85 Torr), typically about 10.66kPa (about 80 Torr). It should be noted that this pressure is considerably higher than prior art CVD tungsten deposition processes where the pressure rarely exceeded 0.133kPa (1 Torr). This higher pressure results in markedly faster deposition rates which, as will be discussed below, may be as much as an order of magnitude greater than prior art tungsten deposition rates. The higher pressure of the process of the invention also is beneficial in the increase of reflectivity of the surface of the deposited tungsten layer. The use of such high pressures, in accordance with the invention, may be of further interest with respect to adjustment of the stress formed in the CVD deposited tungsten layer by permitting more adjustment of the WF 6 and H 2 flow rates as well as the flow rate of the diluent gas due to the higher overall flow rates of the gases in the mixture. While we do not wish to be bound by any theories of operation of the process, it may also be that the higher flow rates are changing the growth mechanism of the layer which may change the mechanical stress on the tungsten layer. The temperature of the susceptor, i.e., the wafer support plate, in the chamber is maintained in a range of from about 350°C to about 525°C, preferably in a range of from about 450°C to about 475°C during the deposition. The deposition time will vary with the desired thickness of tungsten layer 40. The tungsten deposition rate of the process of the invention, which is faster than the prior art deposition rates by as much as a order of magnitude, may vary from about 200 to about 700 nm (about 2000 to about 7000 Å) per minute. For example, to deposit a tungsten layer of from about 0.8 µm to about 1.5 µm typical about 1 µm , utilizing the process of the invention, the deposition time may vary from about 2 to about 7 minutes. The deposition may be carried out in any commercially available CVD deposition equipment capable of being operated within the temperature and pressure ranges discussed above. An example of such commercially available equipment is the Precision 5000 multichamber deposition and etching system available from Applied Materials, Inc. in Santa Clara, CA. A multi-chambered apparatus of this type which may be used in the practice of this invention is described and claimed in Toshima U.S. Patent 4,785,962, assigned to the assignee of this application and cross-reference to which is hereby made. In such an apparatus, wherein the gas distribution inlet or "showerhead" distance from the wafer may be adjusted, the wafer may be spaced from the gas inlet a distance of from about 5.08 to 15.24 mm (about 200 to 600 mils), preferably about 7.62 to 12.7 mm (about 300 to 500 mils), typically about 10.16 mm (about 400 mils). However, the spacing, at least within the 7.62 to 12.7 mm (300 to 500 mils) range, has not been found to be critical to the operation of the process of the invention. In yet another embodiment of the process of the invention, a nucleation layer is formed over the intermediate layer prior to deposition of the tungsten layer. The purpose of this nucleation layer is to provide a layer of growth sites to promote uniform deposition of a tungsten layer thereon. The need for such a nucleation layer will vary, depending upon the materials used in forming the intermediate layer. When sputtered tungsten or sputtered titanium tungsten comprises the intermediate layer, the need for formation of a nucleation layer is diminished and may be dispensed with entirely, if desired. However, when the intermediate layer comprises a titanium nitride layer, it is important to form the nucleation layer prior to deposition of the tungsten layer, in accordance with the practice of this embodiment of the invention, since a layer of CVD tungsten deposited directly over a titanium nitride layer (without the nucleation layer of the invention) has been found to have as much as a 10-15% difference in thickness and resistivity over the entire layer. To form the nucleation layer in accordance with the practice of the process of the invention, a semiconductor wafer, which may have insulating and intermediate layers formed thereon, as described above, is placed in a CVD apparatus such as previously described and a mixture of gases which includes silane (SiH 4 ) is flowed into the chamber. The flowing mixture of gases will include from about 5 to about 50 sccm of WF 6 , from about 5 to about 50 sccm of SiH 4 , from about 500 to about 3000 sccm of Ar, and from about 20 to about 300 sccm of N 2 . As in the tungsten deposition process already described, the pressure in the vacuum chamber is maintained at from about 2.66kPa to about 101.3kPa (about 20 to about 760 Torr),preferably from about 7.99 to about 10.66 kPa (about 60 to about 80 Torr), and most preferably from about 10 to about 11.3kPa (about 75 to about 85 Torr), typically about 10.66 kPa (about 80 Torr), while the susceptor temperature is maintained in a range of from about 350°C to about 525°C, preferably in a range of from about 450°C to about 475°C. Growth of a sufficient thickness of the nucleation layer, i.e., from about 20 to about 100 nm (about 200 to about 1000 Å), will occur in about 5 to about 20 seconds under the above conditions. While a thicker layer may be deposited by extending the process time, such is unnecessary for the purposes intended, i.e., to promote a more uniform deposition of the tungsten layer. The following examples will serve to further illustrate the process of the invention. Example I A 150 mm (6") diameter silicon wafer, having a layer of titanium nitride previously formed thereon over a silicon oxide layer, was placed in a CVD vacuum chamber maintained at a pressure of 80 Torr and a susceptor temperature of 450°C. A mixture of gases comprising 1000 sccm of Ar, 20 sccm of SiH 4 , 20 sccm of WF 6 , and 50 sccm of N 2 were flowed into the chamber for a period of about 10 seconds from an outlet spaced 10.16 mm (400 mils) from the wafer to deposit about 50 nm (500 Å) of a nucleation layer on the wafer. Example II The wafer coated with the nucleation layer in Example I, together with similar sized silicon wafers, respectively coated with sputtered tungsten and sputtered titanium tungsten over silicon oxide, but without a nucleation layer, were individually placed in a CVD vacuum chamber under the same pressure, temperature, and gas outlet spacing conditions as described in Example I and a gaseous mixture of 1500 sccm of Ar, 1000 sccm of H 2 , 30 sccm of WF 6 , and 50 sccm of N 2 were flowed into the chamber for a time period of about 3 minutes. When each of the wafers was removed, it was examined to determine the properties of the resulting tungsten layer. Each wafer was found to have a uniform layer of tungsten deposited thereon of about 900 nm (9000 Å) thickness (indicating a deposition rate of about 300 nm (3000 Å) per minute) with less than 2% variation in coating thickness, as measured by the resistivity of the layer. The respective reflectivity of the surface of the tungsten layers was found to be 100% for each tungsten layer, compared to the reflectivity of a silicon surface. The resistivity of each of the tungsten layers was measured at about 8.5 micro ohm centimeters, and the stress was measured at about 6·10 4 N/cm 2 (about 6 x 10 9 dynes/cm 2 ). Example III To further illustrate the process of the invention, a 15.24 cm (6") wafer having a sputtered titanium tungsten layer thereon, similar to one of the wafers used in Example II, was placed in the same CVD vacuum chamber under the same conditions except that nitrogen was not included in the gas mixture flowing into the CVD chamber. The wafer was then removed and examined. The reflectivity of the tungsten surface was measured and found to be 60% of the reflectivity of silicon. The resistivity was measured at 9 micro ohm centimeters and the stress was measured at 9·10 4 N/cm 2 (9 x 10 9 dynes/cm 2 ). Example IV Another wafer, identical to one of the wafers used in Example II, was placed in the CVD vacuum chamber and processed under identical conditions to those of Examples II and III except that the temperature was raised to 475°C, and the Ar and H 2 gas flow rates were respectively raised to 2500 sccm and 1500 sccm. The process was carried out for about 3 minutes and about 900 nm (about 9000 Å) of tungsten was deposited. The reflectivity of the tungsten surface was measured and found to be at least 100% The deposition rate, therefore, was the same as in Example II, i.e., about 300 nm (about 3000 Å) per minute. The stress of the resulting tungsten layer was measured at about 1-2·10 4 N/cm 2 (about 1-2 x 10 9 dynes/cm 2 ). Example V To illustrate the effect of the high pressure used in the process as opposed to a lower process, a 15.24 cm (6") diameter wafer was identically processed as in Example II except that the pressure was lowered from 10.66kPa (80 Torr) down to only 1.33kPa (10 Torr). The resultant tungsten layer had a reflectivity which was only 20% that of silicon. Thus, the invention provides an improved process for the formation of a tungsten layer on a semiconductor wafer wherein the deposition rate and the reflectivity are improved by carrying out the deposition process at a markedly higher pressure than the prior art, the reflectivity is also improved by the presence of nitrogen in the gases used in the deposition, and the formation of a nucleation layer enhances the uniformity of the tungsten layer, particularly when used over a titanium nitride layer.

Claims: A CVD process for the deposition of a layer of tungsten on a semiconductor wafer in a vacuum chamber in the presence of nitrogen gas characterized in that the tungsten is deposited on a semiconductor wafer at a pressure of from about 2.66 kPa to 101.3 kPa (about 20 to 760 Torr). A process according to claim 1 wherein a nucleation layer is formed on the semiconductor wafer prior to the layer of tungsten by contacting said wafer with a mixture of WF 6 , N 2 , Ar, and SiH 4 gases in a vacuum chamber to improve the uniformity of the deposited layer of tungsten. The process of claim 2, wherein said nucleation layer is formed by contacting said wafer with a mixture of gases flowing through said vacuum chamber to form said nucleation layer, said mixture of gases comprising: (i) from 5 to 50 sccm WF 6 ; (ii) from 500 to 3000 sccm Ar; (iii) from 20 to 300 sccm N 2 , and (iv) from 5 to 50 sccm SiH 4 . The process of claim 2, wherein during the deposition of tungsten 10 to 300 sccm of nitrogen is flowed through said vacuum chamber to improve the reflectivity of the resulting layer of tungsten. The process of claim 4 wherein during deposition of tungsten a mixture of gases is flowing through the vacuum chamber additionally comprising: (i) WF 6 preferably in an amount from 20 to 200 sccm and/or (ii) Ar preferably in an amount from 100 to 5000 sccm and/or (iii) H 2 preferably in an amount from 300 to 3000 sccm, most preferably 2000 sccm. The process of one of the preceding claims in which during the process the pressure of the vacuum chamber is kept from 2.66 kPa to 101.3 kPa (20 to 760 Torr), preferably 7.99 to 13.33 kPa (60 to 100 Torr) and most preferably 10 kPa to 11.3 kPa (75 to 85 Torr). The process of one of the preceding claims in which the susceptor temperature in the vacuum chamber is from 300°C to 525°C preferably from 450°C to 475°C during said tungsten depositing step.

Inventors: CHANG MEI, CHENG DAVID, LEUNG CISSY, WANG DAVID NIN-KOU, CHANG, MEI, CHENG, DAVID, LEUNG, CISSY, WANG, DAVID NIN-KOU
Applicants: APPLIED MATERIALS INC, APPLIED MATERIALS, INC.
Application year: 1990
Main classification: H01L21
IPC codes: C23C16, H01L21