# Patent

## Title
Tungsten nitride atomic layer deposition processes

## Abstract

In one embodiment, a method for forming a tungsten barrier material on a substrate is provided which includes depositing a tungsten layer on a substrate during a vapor deposition process and exposing the substrate sequentially to a tungsten precursor and a nitrogen precursor to form a tungsten nitride layer on the tungsten layer. Some examples provide that the tungsten layer may be deposited by sequentially exposing the substrate to the tungsten precursor and a reducing gas (e.g., diborane or silane) during an atomic layer deposition process. The tungsten layer may have a thickness of about 50 Å or less and tungsten nitride layer may have an electrical resistivity of about 380 μΩ-cm or less. Other examples provide that a tungsten bulk layer may be deposited on the tungsten nitride layer by a chemical vapor deposition process.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. Ser. No. 11/003,020, filed Dec. 1, 2004, and issued as U.S. Pat. No. 7,115.499, which is a continuation of U.S. Ser. No. 10/084,767, filed Feb. 26, 2002, and issued as U.S. Pat. No. 6,833,161, each of which is herein incorporated by reference in its entirety.


BACKGROUND OF THE INVENTION
1. Field of the Invention
Embodiments of the present invention relate to a method for manufacturing integrated circuit devices. More particularly, embodiments of the invention relate to forming stoichiometric tungsten nitride films using cyclic or atomic layer deposition.
2. Description of the Related Art
Semiconductor device geometries have dramatically decreased in size since such devices were first introduced several decades ago and are continually decreasing in size today. Metal gates made of tungsten are becoming important because of the resistance requirements of these smaller devices. Tungsten is a desirable material because it is widely available and has a lower resistivity and lower contact resistance compared to other conductive metals.
One drawback to using tungsten in a metal gate, however, is that a barrier layer is typically required between silicon and the tungsten to prevent the formation of tungsten silicide. Tungsten silicide has a higher resistivity than tungsten and thus, increases the overall resistance of the gate. Barrier layers, however, also increase the resistance of the device and are deposited in amounts greater than needed due to the inherent limitations of conventional deposition techniques.
Bulk deposition processes, such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), are conventionally used to deposit barrier layers. Bulk deposition processes are high deposition rate processes that maintain certain deposition conditions for a period of time to deposit material having a desired thickness, typically greater than 1,000 Å. This time period varies depending on the dynamics of the reaction and can be complicated where a reaction condition must be maintained for a brief period of time in order to deposit a controllable and repeatable thin layer of material.
There is a need, therefore, for new methods for depositing controllable, repeatable, and thin barrier layers.
SUMMARY OF THE INVENTION
Embodiments of the invention include a method for forming a tungsten nitride layer by alternately pulsing a tungsten-containing compound and a nitrogen-containing compound until a tungsten nitride layer having a thickness of about 100 Å or less is formed.
Embodiments of the invention also include a method for forming a tungsten layer comprising depositing a tungsten nitride barrier layer by alternately pulsing a first tungsten-containing compound and a nitrogen-containing compound, and depositing a tungsten layer by alternately pulsing a second tungsten-containing compound and a reducing compound.
Embodiments of the invention further include a method for forming a tungsten layer, comprising depositing a tungsten nitride barrier layer by alternately pulsing a first tungsten-containing compound and a nitrogen-containing compound, and depositing a tungsten layer on the barrier layer. In one aspect, the tungsten layer is deposited by chemical vapor deposition or physical vapor deposition techniques. In another aspect, the tungsten layer is deposited by alternately pulsing a second tungsten-containing compound and a reducing compound. In yet another aspect, the tungsten layer is deposited by alternately pulsing the second tungsten-containing compound and the reducing compound to form a pre-layer having a thickness of about 50 Å or less followed by bulk tungsten deposition using chemical vapor deposition or physical vapor deposition.



BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
FIG. 1 depicts a schematic cross-sectional view of a process chamber that can be used to practice embodiments described herein.
FIG. 2 illustrates a process sequence for the formation of a tungsten nitride barrier layer using a cyclical deposition technique according to one embodiment described herein.
FIG. 3 illustrates a process sequence for the formation of a tungsten nitride layer using a cyclical deposition technique according to another embodiment described herein.
FIG. 4 illustrates a process sequence for the formation of a tungsten nitride layer using a cyclical deposition technique according to another embodiment described herein.
FIG. 4A illustrates a process sequence for the formation of a tungsten nitride layer particularly on a silicon surface using a cyclical deposition technique according to another embodiment described herein.
FIG. 5 shows a cross sectional view of an exemplary metal oxide gate device 10 utilizing a tungsten nitride layer according to the present invention.
FIG. 6 shows a cross sectional view of a conventional DRAM device utilizing a tungsten nitride layer deposited according to an embodiment of a cyclical deposition technique described herein.
FIG. 7 shows an Auger profile showing the atomic concentration of the deposited tungsten nitride layer.



DETAILED DESCRIPTION
A tungsten nitride layer (WxNy) having a thickness less than 100 Å, such as about 20 Å or less, is formed using embodiments of a cyclical deposition technique described herein. The tungsten nitride layer has a resistivity of about 380 μΩ-cm or less, and provides excellent barrier properties for various device applications, such as an electrode in either DRAM or capacitors for example, without subsequent thermal treatment. The tungsten nitride layer also has a significantly reduced fluorine concentration compared to tungsten nitride layers deposited by conventional bulk deposition techniques, such as plasma enhanced chemical vapor deposition (PECVD). The tungsten nitride layer is particularly useful for devices having dimensions of 0.15 microns or less, such as 100 nm (nanometers).
“Cyclical deposition” as used herein refers to the sequential introduction of two or more reactive compounds to deposit a mono layer of material on a substrate surface. The two or more reactive compounds are sequentially introduced into a reaction zone of a processing chamber. Each reactive compound is separated by a delay/pause to allow each compound to adhere and/or react on the substrate surface. In one aspect, a first precursor or compound A is dosed/pulsed into the reaction zone followed by a first time delay/pause. Next, a second precursor or compound B is dosed/pulsed into the reaction zone followed by a second delay. The reactive compounds are alternatively pulsed until a desired film or film thickness is formed on the substrate surface.
In one aspect, a tungsten nitride layer is deposited on a substrate surface by alternately adsorbing a tungsten-containing compound and a nitrogen-containing compound on a substrate surface. The term “compound” is intended to include one or more precursors, reductants, reactants, and catalysts. Each compound may be a single compound or a mixture/combination of two or more compounds. During deposition, the substrate should be maintained at a temperature of about 550° C. or more, such as between 550° C. and 700° C., at a process chamber pressure of between about 1 Torr and about 10 Torr. The tungsten-containing compound is introduced to the substrate surface at a rate between about 1 sccm (standard cubic centimeters per minute) and about 400 sccm, such as between about 10 sccm and about 100 sccm, and pulsed for about 1 second or less, such as about 0.2 seconds or less. The nitrogen-containing compound is introduced to the substrate surface at a rate between about 5 sccm to about 150 sccm, such as between about 5 sccm and about 25 sccm, and thereafter pulsed for about 1 second or less, such as about 0.2 seconds or less. In one aspect, argon is continuously provided as a carrier/purge gas at a rate between about 250 sccm and about 1,000 sccm, such as between about 500 sccm and about 750 sccm. Each cycle, consisting of a pulse of the tungsten-containing compound and a pulse of the nitrogen-containing compound, forms between about 2 Å to about 3 Å of tungsten nitride, such as about 2.5 Å.
A “substrate surface”, as used herein, refers to any substrate surface upon which film processing is performed. For example, a substrate surface may include silicon, silicon oxide, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal alloys, and other conductive materials, depending on the application. A substrate surface may also include dielectric materials such as silicon dioxide and carbon doped silicon oxides.
FIG. 1 illustrates a schematic, partial cross section of an exemplary processing chamber 16 useful for depositing a tungsten nitride layer according to each of the embodiments of the present invention. Such a processing chamber 16 is available from Applied Materials, Inc. located in Santa Clara, Calif., and a brief description thereof follows. A more detailed description may be found in commonly assigned U.S. Ser. No. 10/016,300, filed on Dec. 12, 2001, and issued as U.S. Pat. No. 6,878,206, which is incorporated herein by reference.
The processing chamber 16 may be integrated into an integrated processing platform, such as an Endura SL platform also available from Applied Materials, Inc. Details of the Endura SL platform are described in commonly assigned U.S. Ser. No. 09/451,628, entitled “Integrated Modular Processing Platform,” filed on Nov. 30, 1999, which is incorporated herein by reference.
Referring to FIG. 1, the processing chamber 16 includes a chamber body 14, a lid assembly 20 for gas delivery, and a thermally controlled substrate support member 46. The thermally controlled substrate support member 46 includes a wafer support pedestal 48 connected to a support shaft 48a. The thermally controlled substrate support member 46 may be moved vertically within the chamber body 14 so that a distance between the support pedestal 48 and the lid assembly 20 may be controlled. An example of a lifting mechanism for the support pedestal 48 is described in detail in U.S. Pat. No. 5,951,776, which is hereby incorporated by reference in its entirety.
The support pedestal 48 includes an embedded thermocouple 50a that may be used to monitor the temperature thereof. For example, a signal from the thermocouple 50a may be used in a feedback loop to control power applied to a heater element 52a by a power source 52. The heater element 52a may be a resistive heater element or other thermal transfer device disposed in or in contact with the pedestal 48 utilized to control the temperature thereof. Optionally, the support pedestal 48 may be heated using a heat transfer fluid (not shown).
The support pedestal 48 may be formed from any process-compatible material, including aluminum nitride and aluminum oxide (Al2O3 or alumina) and may also be configured to hold a substrate thereon employing a vacuum, i.e., support pedestal 48 may be a vacuum chuck. Using a vacuum check, the support pedestal 48 may include a plurality of vacuum holes (not shown) that are placed in fluid communication with a vacuum source routed through the support shaft 48a. 
The chamber body 14 includes a liner assembly 54 having a cylindrical portion and a planar portion. The cylindrical portion and the planar portion may be formed from any suitable material such as aluminum, ceramic and the like. The cylindrical portion surrounds the support pedestal 48. The cylindrical portion also includes an aperture 60 that aligns with the slit valve opening 44 disposed a sidewall 14b of the housing 14 to allow entry and egress of substrates from the chamber 16.
The planar portion of the liner assembly 54 extends transversely to the cylindrical portion and is disposed against a chamber bottom 14a of the chamber body 14. The liner assembly 54 defines a chamber channel 58 between the chamber body 14 and both the cylindrical portion and planar portion of the liner assembly 54. Specifically, a first portion of channel 58 is defined between the chamber bottom 14a and planar portion of the liner assembly 54. A second portion of channel 58 is defined between the sidewall 14b of the chamber body 14 and the cylindrical portion of the liner assembly 54. A purge gas is introduced into the channel 58 to minimize unwanted deposition on the chamber walls and to control the rate of heat transfer between the chamber walls and the liner assembly 54.
The chamber body 14 also includes a pumping channel 62 disposed along the sidewalls 14b thereof. The pumping channel 62 includes a plurality of apertures, one of which is shown as a first aperture 62a. The pumping channel 62 includes a second aperture 62b that is coupled to a pump system 18 by a conduit 66. A throttle valve 18a is coupled between the pumping channel 62 and the pump system 18. The pumping channel 62, the throttle valve 18a, and the pump system 18 control the amount of gas flow from the processing chamber 16. The size, number, and position of the apertures 62a in communication with the chamber 16 are configured to achieve uniform flow of gases exiting the lid assembly 20 over the support pedestal 48 having a substrate disposed thereon.
The lid assembly 20 includes a lid plate 20a having a gas manifold 34 mounted thereon. The lid plate 20a provides a fluid tight seal with an upper portion of the chamber body 14 when in a closed position. The gas manifold 34 includes a plurality of control valves 32c (only one shown) to provide rapid and precise gas flow with valve open and close cycles of less than about one second, and in one embodiment, of less than about 0.1 seconds. The valves 32c are surface mounted, electronically controlled valves. One valve that may be utilized is available from Fujikin of Japan as part number FR-21-6.35 UGF-APD. Other valves that operate at substantially the same speed and precision may also be used.
The lid assembly 20 further includes a plurality of gas sources 68a, 68b, 68c, each in fluid communication with one of the valves 32c through a sequence of conduits (not shown) formed through the chamber body 14, lid assembly 20, and gas manifold 34.
The processing chamber 16 further includes a reaction zone 100 that is formed within the chamber body 14 when the lid assembly 20 is in a closed position. Generally, the reaction zone 100 includes the volume within the processing chamber 16 that is in fluid communication with a wafer 102 disposed therein. The reaction zone 100, therefore, includes the volume downstream of each valve 32c within the lid assembly 20, and the volume between the support pedestal 48 and the lower surface of the lid plate 20. More particularly, the reaction zone 100 includes the volume between the outlet of the dosing valves 32c and an upper surface of the wafer 102.
A controller 70 regulates the operations of the various components of the processing chamber 16. The controller 70 includes a processor 72 in data communication with memory, such as random access memory 74 and a hard disk drive 76 and is in communication with at least the pump system 18, the power source 52, and the valve 32c. 
Software routines are executed to initiate process recipes or sequences. The software routines, when executed, transform the general purpose computer into a specific process computer that controls the chamber operation so that a chamber process is performed. For example, software routines may be used to precisely control the activation of the electronic control valves for the execution of process sequences according to the present invention. Alternatively, the software routines may be performed in hardware, as an application specific integrated circuit or other type of hardware implementation, or a combination of software or hardware.
Barrier Layer Formation
FIG. 2 illustrates a process sequence 200 for depositing a tungsten nitride layer according to one embodiment of the present invention. As shown in step 202, a substrate is provided to the process chamber. The process chamber conditions, such as the temperature and pressure, for example, are adjusted to enhance the adsorption of the process gases on the substrate. The substrate should be maintained at a temperature of about 550° C. or more, such as between 550° C. and 700° C., at a process chamber pressure of between about 1 Torr and about 10 Torr.
A constant carrier gas stream is established within the process chamber as indicated in step 204. Carrier gases may be selected to also act as a purge gas for the removal of volatile reactants and/or by-products from the process chamber. Carrier gases such as, for example, helium (He), argon (Ar), nitrogen (N2), hydrogen (H2), among others, and combinations thereof may be used. In one aspect, argon is continuously provided at a rate between about 250 sccm and about 1,000 sccm, such as between about 500 sccm and about 750 sccm.
Referring to step 206, after the carrier gas stream is established within the process chamber, a pulse of a tungsten-containing compound is added to the carrier gas stream. A “dose/pulse” as used herein is intended to refer to a quantity of a particular compound that is intermittently or non-continuously introduced into a reaction zone of a processing chamber. The quantity of a particular compound within each pulse may vary over time, depending on the duration of the pulse.
The duration of the pulse of the tungsten-containing compound is variable depending upon a number of factors such as, for example, the volume capacity of the process chamber employed, the vacuum system coupled thereto, and the volatility/reactivity of the particular precursor itself. For example, the tungsten-containing compound is introduced to the substrate surface at a rate between about 1 sccm (standard cubic centimeters per minute) and about 400 sccm, such as between about 10 sccm and about 100 sccm, and pulsed for about 1 second or less, such as about 0.2 seconds or less. More generally, the process conditions are advantageously selected so that a pulse of tungsten-containing compound provides a sufficient amount of volume to absorb at least a monolayer of the tungsten-containing material on the substrate. Thereafter, excess tungsten-containing compound remaining in the chamber is removed from the process chamber by the constant carrier gas stream in combination with the vacuum system.
In step 208, a pulse of a nitrogen-containing compound is added to the carrier gas stream after the excess tungsten-containing compound has been removed from the process chamber. The pulse of nitrogen-containing compound also lasts for a predetermined time that is variable depending upon a number of factors such as, for example, the volume capacity of the process chamber employed, the vacuum system coupled thereto and the volatility/reactivity of the particular precursor itself. For example, the nitrogen-containing compound is introduced to the substrate surface at a rate between about 5 sccm to about 150 sccm, such as between about 5 sccm and about 25 sccm, and thereafter pulsed for about 1 second or less, such as about 0.2 seconds or less. More generally, the duration of the pulse of nitrogen-containing compound should be long enough to adsorb at least a monolayer of the nitrogen-containing compound on the tungsten-containing material. Thereafter, excess nitrogen-containing compound remaining in the chamber is removed by the constant carrier gas stream in combination with the vacuum system.
The duration of each of the pulses of tungsten-containing compound and nitrogen-containing compound may also vary depending on the device geometry, the desired stoichiometry of the deposited layer, and the application of the deposited layer, for example. In one aspect, the duration of the pulse of tungsten-containing compound may be identical to the duration of the pulse of nitrogen-containing compound. In another aspect, the duration of the pulse of tungsten-containing compound may be shorter than the duration of the pulse of nitrogen-containing compound. In still another aspect, the duration of the pulse of tungsten-containing compound may be longer than the duration of the pulse of nitrogen-containing compound.
Additionally, the delays between each pulse of tungsten-containing compound and each pulse of nitrogen-containing compound may have the same duration. That is the duration of the period of non-pulsing between each pulse of the tungsten-containing compound and each pulse of the nitrogen-containing compound can be identical. For such an embodiment, a time interval of non-pulsing between the pulse of the tungsten-containing compound and the pulse of the nitrogen-containing compound is equal to a time interval of non-pulsing between the pulse of the nitrogen-containing compound and the pulse of the tungsten-containing precursor. During the time periods of non-pulsing only the constant carrier gas stream is provided to the process chamber.
The delays between each pulse of tungsten-containing compound and each pulse of nitrogen-containing compound may also have different durations. For example, the duration of the period of non-pulsing between each pulse of the tungsten-containing compound and each pulse of the nitrogen-containing compound may be shorter or longer than the duration of the period of non-pulsing between each pulse of the nitrogen-containing compound and the tungsten-containing precursor. For such an embodiment, a time interval of non-pulsing between the pulse of the tungsten-containing compound and the pulse of the nitrogen-containing compound is different from a time interval of non-pulsing between the pulse of the nitrogen-containing compound and the pulse of the tungsten-containing precursor. During the time periods of non-pulsing, only the constant carrier gas stream is provided to the process chamber.
Additionally, the time intervals for each pulse of the tungsten-containing precursor, the nitrogen-containing compound and the periods of non-pulsing therebetween for each deposition cycle may have the same duration. For such an embodiment, a time interval (T1) for the tungsten-containing precursor, a time interval (T2) for the nitrogen-containing compound, a time interval (T3) of non-pulsing between the pulse of the tungsten-containing compound and the pulse of the nitrogen-containing compound and a time interval (T4) of non-pulsing between the pulse of the nitrogen-containing compound and the pulse of the tungsten-containing compound each have the same value for each deposition cycle. For example, in a first deposition cycle (C1), a time interval (T1) for the pulse of the tungsten-containing compound has the same duration as the time interval (T1) for the pulse of the tungsten-containing compound in a second deposition cycle (C2). Similarly, the duration of each pulse of the nitrogen-containing compound and the periods of non-pulsing between the pulse of the tungsten-containing compound and the nitrogen-containing compound in deposition cycle (C1) is the same as the duration of each pulse of the nitrogen-containing compound and the periods of non-pulsing between the pulse of the tungsten-containing compound and the nitrogen-containing compound in deposition cycle (C2), respectively.
Additionally, the time intervals for at least one pulse of tungsten-containing precursor, at least one pulse of nitrogen-containing compound, and the delays therebetween for one or more of the deposition cycles of the tungsten deposition process may have different durations. For such an embodiment, one or more of the time intervals (T1) for the pulses of the tungsten-containing precursor, the time intervals (T2) for the pulses of the nitrogen-containing compound, the time intervals (T3) of non-pulsing between the pulse of the tungsten-containing compound and the pulse of the nitrogen-containing compound and the time intervals (T4) of non-pulsing between the pulse of the nitrogen-containing compound and the pulse of the tungsten-containing compound may have different values for one or more deposition cycles of the tungsten deposition process. For example, in a first deposition cycle (C1), the time interval (T1) for the pulse of the tungsten-containing compound may be longer or shorter than the time interval (T1) for the pulse of the tungsten-containing compound in a second deposition cycle (C2). Similarly, the duration of each pulse of the nitrogen-containing compound and the periods of non-pulsing between the pulse of the tungsten-containing compound and the nitrogen-containing compound in deposition cycle (C1) may be the same or different than the duration of each pulse of the nitrogen-containing compound and the periods of non-pulsing between the pulse of the tungsten-containing compound and the nitrogen-containing compound in deposition cycle (C2), respectively.
Referring to step 210, after each deposition cycle (steps 204 through 208) a thickness of tungsten nitride will be formed on the substrate. Depending on specific device requirements, subsequent deposition cycles may be needed to achieve a desired thickness. As such, steps 206 and 208 can be repeated until the desired thickness for the tungsten nitride layer is achieved. Thereafter, when the desired thickness is achieved the process is stopped as indicated by step 212. About 2 Å to about 3 Å of tungsten nitride, such as about 2.5 Å, are formed per cycle.
Exemplary tungsten-containing precursors for forming such tungsten layers may include tungsten hexafluoride (WF6) and tungsten hexacarbonyl (W(CO)6), among others, as well as a combination thereof.
Exemplary nitrogen-containing compounds may include nitrogen gas (N2), ammonia (NH3), hydrazine (N2H4), monomethyl hydrazine (CH3N2H3), dimethyl hydrazine (C2H6N2H2), t-butyl hydrazine (C4H9N2H3), phenyl hydrazine (C6H5N2H3), 2,2′-azotertbutane ((CH3)6C2N2), ethylazide (C2H5N3), among others, as well as combinations thereof.
In a particular process sequence 300 described with respect to FIG. 3, a tungsten nitride layer is deposited using separate pulses for each of the tungsten-containing compound, the nitrogen-containing compound, and argon. The deposition sequence 300 includes providing a substrate to the process chamber (step 302); heating the substrate to a temperature greater than 550°C., such as between 550°C. and 700°C. at a pressure less than or about 2 Torr (step 304); providing a pulse of tungsten-containing compound (step 306); providing a first pulse of argon (step 308); providing a pulse of nitrogen-containing compound (step 310); providing a second pulse of argon (step 312); and then repeating steps 304 through 312 until a desired thickness of the tungsten nitride layer has been achieved. Thereafter, the process is stopped (step 316) when the desired thickness is achieved. About 2 Å to about 3 Å of tungsten nitride are formed per cycle.
In FIGS. 2-3, the tungsten deposition cycle is depicted as beginning with a pulse of the tungsten-containing compound followed by a pulse of the nitrogen-containing compound. However, the tungsten deposition cycle may start with a pulse of the nitrogen-containing compound followed by a pulse of the tungsten-containing precursor. Regardless of the pulse sequences, each cycle consists of a pulse of the nitrogen-containing compound and a pulse of the tungsten-containing compound, and cycle is repeated until a desired film or film thickness is achieved.
FIG. 4 shows another process sequence 400 particularly useful for depositing a tungsten nitride barrier layer over a silicon surface. In general, a wafer having a silicon surface is exposed to a chlorine-containing compound, such as dichlorosilane (DCS) for example, prior to alternating pulses of a nitrogen-containing compound and a tungsten-containing compound. The DCS pre-treatment step provides a chlorine terminated silicon surface that resists the formation of tungsten silicide during subsequent exposure to a tungsten-containing compound. Tungsten silicide is undesirable because it increases the resistivity and overall contact resistance of the device.
The nitrogen-containing compound is introduced prior to the tungsten-containing compound to prevent the formation of tungsten silicide due to the reaction of tungsten with the silicon surface. It is believed that the nitrogen-containing compound forms one or more atomic layers of SixNy prior to exposure of the tungsten-containing compound. It is then believed that the one or more atomic layers of SixNy react with the tungsten-containing compound to form one or more atomic layers of WSixNy. The one or more atomic layers of WSixNy provide a much more stable device that is resistant to tungsten diffusion/migration. In metal gate applications, for example, tungsten migration is to be avoided because tungsten atoms may diffuse through the polysilicon gate and come into contact with the dielectric layer, thereby shorting the metal gate.
Referring to FIG. 4, the deposition sequence 400 includes providing a substrate to the process chamber (step 402); heating the substrate to a temperature greater than 550° C., such as between 550° C. and 700° C. at a pressure less than or about 2 Torr (step 404); soaking the substrate in DCS for about 5 seconds to about 1 minute (step 406); providing one or more pulses of ammonia (step 408); introducing a continuous carrier gas stream such as argon gas (step 410); providing a pulse of tungsten hexafluoride (step 412); providing a pulse of ammonia (step 414); and then repeating steps 412 through 414 or stopping the deposition process (step 418) depending on whether a desired thickness for the tungsten nitride layer has been achieved (step 416).
FIG. 4A shows an alternative process sequence 450 useful for depositing a tungsten nitride barrier layer over a silicon surface. The sequence 450 includes providing a substrate to the process chamber (step 452); heating the substrate to a temperature greater than 550° C., such as between 550° C. and 700° C. at a pressure less than or about 2 Torr (step 454); soaking the substrate in DCS for about 5 seconds to about 1 minute (step 456); introducing a continuous carrier gas stream such as argon gas (step 458); providing a pulse of ammonia (step 460); providing a pulse of tungsten hexafluoride (step 462); and then repeating steps 460 through 462 or stopping the deposition process (step 466) depending on whether a desired thickness for the tungsten nitride layer has been achieved (step 466).
Tungsten Metal Gate
FIG. 5 shows a cross sectional view of an exemplary metal oxide gate device utilizing a tungsten nitride barrier layer according to the present invention. The device generally includes an exposed gate 510 surrounded by spacers 516 and silicon source/drain areas 520 formed within a substrate surface 512. The spacers 516 typically consist of an oxide, such as SiO2.
The metal gate 510 includes an oxide layer 511, a polysilicon layer 514, a tungsten nitride layer 515, and a tungsten layer 522. The oxide layer 511, such as a SiO2 layer for example, separates the substrate 512 from the polysilicon layer 514. The oxide layer 511 and the polysilicon layer 514 are deposited using conventional deposition techniques.
The tungsten nitride layer 515 is deposited on the polysilicon layer 514 and is deposited using embodiments of a cyclical deposition technique described above with reference to FIGS. 2-4. In a particular embodiment, similar to the sequence described above with reference to FIG. 4, a process sequence for depositing the tungsten nitride layer 515 on the polysilicon layer 514 includes providing a substrate to the process chamber; heating the substrate to a temperature greater than 550° C., such as between 550° C. and 700° C. at a pressure less than or about 2 Torr; soaking the substrate in DCS for about 5 seconds to about 1 minute; providing one or more pulses of ammonia; introducing a continuous carrier gas stream such as argon gas; providing a pulse of tungsten hexafluoride to the reaction zone; providing a pulse of ammonia to the reaction zone; and then repeating the pulses of tungsten hexafluoride and ammonia until a tungsten nitride layer having a thickness less than 100 Å has been formed.
A tungsten layer 522 is then deposited on the tungsten nitride layer 515. Although any metal deposition process, such as conventional chemical vapor deposition or physical vapor deposition for example, may be used, the tungsten layer 522 may be deposited by alternately adsorbing a tungsten-containing compound and a reducing gas, using a cyclical deposition technique similar to one described above with reference to FIGS. 2-4. Suitable tungsten-containing compounds include, for example, tungsten hexafluoride (WF6) and tungsten hexacarbonyl (W(CO)6), among others. Suitable reducing gases include, for example, silane (SiH4), disilane (Si2H6), dichlorosilane (SiCl2H2), borane (BH3), diborane (B2H6), triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nonaborane, decaborane, and combinations thereof.
One exemplary process of depositing a tungsten layer includes sequentially providing pulses of tungsten hexafluoride and pulses of diborane. The tungsten hexafluoride may be provided to an appropriate flow control valve at a flow rate of between about 10 sccm (standard cubic centimeters per minute) and about 400 sccm, such as between about 20 sccm and about 100 sccm, and thereafter pulsed for about 1 second or less, such as about 0.2 seconds or less. A carrier gas, such as argon, is provided along with the tungsten hexafluoride at a flow rate between about 250 sccm to about 1,000 sccm, such as between about 500 sccm to about 750 sccm. The diborane may be provided to an appropriate flow control valve at a flow rate of between about 5 sccm and about 150 sccm, such as between about 5 sccm and about 25 sccm, and thereafter pulsed for about 1 second or less, such as about 0.2 seconds or less. A carrier gas, such as argon, is provided along with the diborane at a flow rate between about 250 sccm to about 1,000 sccm, such as between about 500 sccm to about 750 sccm. The substrate is maintained at a temperature between about 250° C. and about 350° C. at a chamber pressure between about 1 Torr and about 10 Torr.
A more detailed description of tungsten deposition using a cyclical deposition technique may be found in commonly assigned U.S. Ser. No. 10/016,300, filed on Dec. 12, 2001, and issued as U.S. Pat. No. 6,878,206, and in commonly assigned U.S. Ser. No. 10/082,048, entitled “Deposition Of Tungsten Films For Dynamic Random Access Memory (DRAM) Application,” filed on Feb. 20, 2002, and published as U.S. Pub. No. 2003-0157760, which are both incorporated herein by reference in their entirety.
FIG. 6 shows another exemplary use of a tungsten nitride barrier layer. More particularly, FIG. 6 is a cross sectional view of a conventional DRAM device having a transistor 620 positioned adjacent a top portion of a trench capacitor 630. The access transistor 620 for the DRAM device 610 is positioned adjacent a top portion of the trench capacitor 630. Preferably, the access transistor 620 comprises an n-p-n transistor having a source region 622, a gate region 624, and a drain region 626. The gate region 624 comprises a P− doped silicon epi-layer disposed over the P+ substrate. The source region 622 of the access transistor 620 comprises an N+ doped material disposed on a first side of the gate region 624, and the drain region 626 comprises an N+ doped material disposed on a second side of the gate region 624, opposite the source region 622. The source region 622 is connected to an electrode of the trench capacitor.
The trench capacitor 630 generally comprises a first electrode 632, a second electrode 634 and a dielectric material 636 disposed therebetween. The P+ substrate serves as a first electrode 632 of the trench capacitor 630 and is connected to a ground connection. A trench 638 is formed in the P+ substrate and filled with a heavily doped N+ polysilicon which serves as the second electrode 634 of the trench capacitor 630. The dielectric material 636 is disposed between the first electrode 632 (i.e., P+ substrate) and the second electrode 634 (i.e., N+ polysilicon).
In one aspect, the trench capacitor 630 also includes a first tungsten nitride barrier layer 640 disposed between the dielectric material 636 and the first electrode 632. Preferably, a second tungsten nitride barrier layer 642 is disposed between the dielectric material 636 and the second electrode 634. Alternatively, the barrier layers 640, 642 are a combination film, such as W/WN. The barrier layers 640, 642 are deposited utilizing embodiments of the cyclical deposition techniques described herein.
Although the above-described DRAM device utilizes an n-p-n transistor, a P+ substrate as a first electrode, and an N+ polysilicon as a second electrode of the capacitor, other transistor designs and electrode materials are contemplated by the present invention to form DRAM devices. Additionally, other devices, such as crown capacitors for example, are contemplated by the present invention.
Embodiments of depositing a tungsten nitride barrier layer using cyclical deposition techniques described herein will be further described below in the following non-limiting example.
EXAMPLE
A tungsten nitride barrier layer was deposited within a cyclical deposition chamber similar to the chamber described above with reference to FIG. 2. The tungsten nitride barrier layer was deposited on a polysilicon layer. The barrier layer was deposited at about 680° C. and about 1.5 Torr. Argon was continuously introduced into the chamber at about 500 sccm. Pulses of tungsten hexafluoride and ammonia were alternately pulsed into the processing chamber, and 40 cycles were performed. Each pulse of tungsten hexafluoride had a rate of about 3 sccm and a duration of about 5 seconds. Each pulse of ammonia had a rate of about 300 sccm and a duration of about 20 seconds. The time delay between pulses was about 20 seconds. The deposition rate was about 2.5 Å per minute. The resulting tungsten nitride layer had a thickness of about 350 Å.
FIG. 7 shows an Auger profile showing the atomic concentration of the deposited tungsten nitride layer. It was surprisingly found that the cyclical deposition technique provided a substantially stoichiometric W2N layer without the need for an additional thermal anneal post-treatment. Further, the deposited stoichiometric W2N layer had a significantly reduced fluorine concentration compared to plasma enhanced chemical vapor deposition (PECVD) WN. The measured resistivity of the barrier layer was 380 μΩ-cm, which is about 50 percent less than a comparable low pressure chemical vapor deposition (LPCVD) WN layer and about 60 percent less than a PVD WN layer.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

## Claims

1. A The method for forming a tungsten barrier material on a substrate, comprising:
exposing a substrate to a tungsten precursor to form a tungsten layer thereon, wherein the tungsten precursor is selected from the group consisting of tungsten hexafluoride, tungsten carbonyl, and derivatives thereof;
repeatedly exposing the substrate seguentially to the tungsten precursor and a nitrogen precursor to form a tungsten nitride layer on the tungsten layer, wherein the nitrogen precursor is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′-azotertbutane, ethylazide, derivatives thereof, and combinations thereof; and
depositing a tungsten bulk layer over the tungsten nitride layer by a chemical vapor deposition process.

2. A method for forming a tungsten barrier material on a substrate, comprising:
depositing a tungsten layer on a substrate during a vapor deposition process; and
repeatedly exposing the substrate seguentially to a tungsten precursor and a nitrogen precursor to form a tungsten nitride layer on the tungsten layer, wherein the nitrogen precursor is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′-azotertbutane, ethylazide, derivatives thereof, and combinations thereof.

3. The method of claim 2, wherein the nitrogen precursor comprises ammonia.

4. A method for forming a tungsten barrier material on a substrate, comprising:
exposing a substrate to a tungsten precursor to form a tungsten layer thereon; and
repeatedly exposing the substrate seguentially to the tungsten precursor and a nitrogen precursor to form a tungsten nitride layer on the tungsten layer, wherein the nitrogen precursor is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′-azotertbutane, ethylazide, derivatives thereof, and combinations thereof.

5. A method for forming a tungsten barrier material on a substrate, comprising:
exposing a substrate to tungsten hexafluoride to form a tungsten layer thereon; and
repeatedly exposing the substrate sequentially to tungsten hexafluoride and ammonia to form a tungsten nitride layer on the tungsten layer.

6. The method of claim 5, wherein the tungsten nitride layer has an electrical resistivity of about 380 μΩ-cm or less.

7. A method for forming a tungsten barrier material on a substrate, comprising:
exposing a substrate to tungsten hexafluoride to form a tungsten layer thereon;
repeatedly exposing the substrate sequentially to tungsten hexafluoride and ammonia to form a tungsten nitride layer on the tungsten layer; and
depositing a tungsten bulk layer over the tungsten nitride layer by a chemical vapor deposition process.

8. The method of claim 7, wherein the tungsten nitride layer has an electrical resistivity of about 380 μΩ-cm or less.

9. The method of claim 7, wherein the tungsten layer is deposited by sequentially exposing the substrate to the tungsten hexafluoride and diborane.

10. A method for forming a tungsten barrier material on a substrate, comprising:
exposing a substrate to tungsten hexafluoride to form a tungsten layer thereon;
exposing the substrate sequentially to tungsten hexafluoride and ammonia to form a tungsten nitride layer on the tungsten layer, wherein the tungsten nitride layer has an electrical resistivity of about 380 μΩ-cm or less; and
depositing a tungsten bulk layer over the tungsten nitride layer.

11. The method of claim 10, wherein the tungsten nitride layer is deposited by repeatedly exposing the substrate sequentially to the tungsten hexafluoride and ammonia.