Patent Application
20050136657
1. Field of the Invention
The present invention relates to a film-formation method for a semiconductor process, and particularly to a method of forming a film containing a metal element by CVD (chemical vapor deposition) on a target substrate, such as a semiconductor wafer. The term “semiconductor process” used herein includes various kinds of processes which are performed to manufacture a semiconductor device or a structure having wiring layers, electrodes, and the like to be connected to a semiconductor device, on a target substrate, such as a semiconductor wafer or an LCD substrate, by forming semiconductor layers, insulating layers, and conductive layers in predetermined patterns on the target substrate.
2. Description of the Related Art
A semiconductor device with a multi-layered interconnection structure is manufactured by repeating film-formation and pattern-etching on the surface of a semiconductor wafer, such as a silicon substrate. For example, the connecting portion between a silicon substrate and an interconnection layer disposed thereabove, or the connecting portion between upper and lower interconnection layers is provided with a barrier layer to prevent separation of an underlying layer or to prevent materials of laminated layers from causing counter diffusion relative to each other. For example, a TiN film formed by thermal CVD is used as a barrier layer of this kind. There is a case where a thin Ti film is formed by plasma CVD as an underlying film below the TiN film, and a case where no Ti film is formed as the underlying film.
6TiCl4+8NH3→6TiN+24HCl+N2 (1)
When such a film-formation process is repeatedly performed on a plurality of wafers W, TiN is deposited on a wall or the like in the vacuum process chamber 1. For example, as shown in
Conventionally, a pre-coating step is performed, as follows. Specifically, at first, the interior of the vacuum process chamber 1 is vacuum-exhausted, while the worktable is heated to a temperature of 600 to 700° C. After the temperature of the worktable 13 becomes stable, the pressure in the vacuum process chamber 1 is set at 40 Pa (0.3 Torr). Then, TiCl4 gas and NH3 gas are supplied together as process gases into the vacuum process chamber 1, after their flow rates are stabilized by pre-flow. The flow rate of TiCl4 gas is set at, e.g., about 30 to 50 sccm, and the flow rate of NH3 gas at, e.g., about 400 sccm. The two process gases are supplied for a time period of, e.g., about 15 to 20 minutes. Then, in order to perform a post-nitride process, the supply of TiCl4 gas is stopped and only NH3 gas is supplied at a flow rate of about 1000 sccm, while the interior of the vacuum process chamber 1 is vacuum-exhausted, for a predetermined time period of, e.g., several tens of seconds. By doing so, a TiN film (pre-coat) having a thickness of, e.g., about 0.5 to 2.0 μm is formed on the surface of the worktable 13. Then, a wafer W is placed on the pre-coated worktable 13, and a film-formation process is performed so that a Ti film 18 and a TiN film 19 are formed on the surface of the wafer W (see
However, in the film-formation process of a TiN film described above, chlorides are dissociated from TiCl4 gas or produced as by-products in the pre-coating step, and react with metals of the vacuum process chamber 1, thereby producing metal chlorides. The metal chlorides evaporate during the film-formation step, and are taken into a film formed on the wafer W. If an unexpected metal enters the film, the electrical properties of devices to be formed are affected, thereby lowering the yield. Accordingly, the degree of metal contamination has to be controlled, to be as low as possible. However, the thinner the film of a device is, the stricter the permissible level of metal contamination becomes.
An object of the present invention is to provide a film-formation method for a semiconductor process, which can reduce the total amount of contaminants, such as metal, in a main film to be formed on a target substrate after a pre-coating process is performed on a worktable in a process chamber.
According to a first aspect of the present invention, there is provided a film-formation method for a semiconductor process to form a film containing a metal element on a target substrate, which is placed on a worktable in an airtight process chamber, the method comprising:
According to a second aspect of the present invention, there is provided a CVD method of forming a film containing a metal element on a target substrate, which is placed on a worktable in an airtight process chamber, by supplying a first process gas containing the metal element and a second process gas that assists decomposition of the first process gas into the process chamber, the method comprising:
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate presently preferred embodiments of the invention, and together with the general description given above and the detailed description of the preferred embodiments given below, serve to explain the principles of the invention.
In the process of developing the present invention, the inventors studied problems of conventional film-formation methods performed in the CVD apparatus shown in
In a film-formation process of a TiN film, since the inner surface of the process chamber 1 and the surface of the showerhead 15 have lower temperatures than the worktable 13, no or hardly any TiN film is deposited thereon. However, a film may be deposited on the showerhead 15, where the distance between the showerhead 15 and worktable 13 is small. In a film-formation process of a TiN film, TiCl4 gas or a mixture gas of TiCl4 gas and NH3 gas is supplied for a time period as long as, e.g., 15 to 20 minutes. In this case, hydrogen chloride (HCl) is produced due to thermal decomposition of TiCl4 gas, or reaction between TiCl4 gas and NH3 gas. HCl then reacts with the surface portion of metal components of the process chamber 1 or the like, thereby producing a lot of metal chlorides. When a film-formation process is performed on a wafer W, the metal chlorides disperse and are taken into a thin film formed on the wafer W; which is one of the causes behind the rise in metal contaminants.
There are processes other than TiN film formation, which also suffer this problem, i.e., wherein a metal compound is produced during a pre-coating step, and thus a metal contaminant is taken into a thin film formed on a wafer W. For example, where a Ta2O5 film is formed by the reaction of PET (pentoethoxytantalum) with O2 gas, a pre-coat is formed on the surface of a worktable. In this case, metal chlorides stable in the process chamber react with a process gas used in a pre-coating step, and produce unstable substances, which disperse in the process chamber. The metal chlorides are believed to have been produced due to the reaction of ClF3 gas used in a cleaning step with the surface portion of metal components of the process chamber 1 or the like.
Embodiments of the present invention achieved on the basis of the findings given above will now be described with reference to the accompanying drawings. In the following description, the constituent elements having substantially the same function and arrangement are denoted by the same reference numerals, and a repetitive description will be made only when necessary.
A worktable (susceptor) 32 is disposed in the process chamber 21. The worktable 32 is formed of a circular plate, whose bottom is supported by a strut 31 extending upward from the bottom of the exhaust pit 23. The worktable 32 is made of a ceramic material, such as aluminum nitride (AlN). The top surface of the worktable 32 is set to be slightly larger than a target substrate or wafer W, and to place the wafer W substantially horizontally thereon. A guide ring 33 made of, e.g., alumina (Al2O3) is disposed on the periphery of the worktable 32, for guiding a wafer W and covering the transit portion of the worktable 32 from the top surface to the side surface.
A heater 34 formed of, e.g., a resistance heating body is built in the worktable 32. The heater 34 is temperature-controlled by, e.g., a power supply 35 disposed outside the process chamber 21 in accordance with intended purpose. Thus, the heater 34 uniformly heats the surface of a wafer W in a film-formation step, or heats the worktable surface to a predetermined temperature in a pre-coating step, as described later.
The worktable 32 is provided with lift pins 36 (for example, three pins in practice) for transferring a wafer W relative to a transfer arm (not shown), which enters through the gate valve 26. The lift pins 36 can project from and retreat into the worktable 32. The lift pins 36 are moved up and down by an elevating mechanism 38 through a support member 37 that supports their bottoms.
A showerhead 4 is disposed on the ceiling of the process chamber 21 through an insulating member 41. The showerhead 4 has a post-mix type structure, which prevents two different gases from mixing with each other inside the showerhead 4, while it supplies the gases individually uniformly toward the worktable 32. The showerhead 4 includes three plate parts (upper part 4a, middle part 4b, and lower part 4c) made of, e.g., aluminum or nickel, and arrayed in the vertical direction. A first flow passage 42 connected to a first gas supply line 5a and a second flow passage 43 connected to a second gas supply line 5b are separately formed in the parts 4a, 4b, and 4c. The first and second flow passages 42 and 43 communicate with gas delivery holes 44 and 45 formed in the bottom surface of the lower part 4c through gas diffusion spaces formed between the parts.
The first and second gas supply lines 5a and 5b are fed with respective gases from a gas supply mechanism 50 disposed on the upstream side. The gas supply mechanism 50 includes a cleaning gas supply source 51, a film-formation gas supply source 52, a first carrier gas supply source 53, an ammonia gas supply source 54, and a second carrier gas supply source 55. The cleaning gas supply source 51 supplies a cleaning gas, such as ClF3 gas. The film-formation gas supply source 52 supplies titanium tetrachloride (TiCl4) gas, which is a process gas containing Ti used as a film-formation component. The first carrier gas supply source 53 supplies a carrier gas, such as an inactive gas, e.g., nitrogen (N2) gas, used for supplying TiCl4 gas. The ammonia gas supply source 54 supplies ammonia (NH3) gas. The second carrier gas supply source 55 supplies a carrier gas, such as N2 gas, used for supplying NH3 gas.
The lines of the gas supply mechanism 50 are provided with valves V1 to V10 and mass-flow controllers M1 to M5. The first gas supply line 5a has a branch to a bypass line 5c for directly exhausting gas to the exhaust line 24, bypassing the process chamber 21. Valves Va and Vc are switched for gas to flow through the process chamber 21 or the bypass line 5c.
As described later, NH3 gas is used as “a process gas for forming a segment film” and also as “a process gas for removing a metal chloride” in a pre-coating process. TiCl4 gas corresponds to “a process gas containing a metal compound” as well as “a process gas or compound containing a metal and a halogen element.”
The showerhead 4 is connected to an RF (Radio Frequency) power supply 47 through a matching device 46. The RF power supply 47 is used to turn a film-formation gas, supplied to a wafer W, into plasma during a film-formation process, thereby accelerating a film-formation reaction. A control section 200, such as a computer, is arranged to control adjustment on the members constituting the film-formation apparatus, such as drive of the elevating mechanism 38, output of the power supply 35, the exhaust rate of the vacuum-exhaust section 25, and the gas supply/stop and flow rate of the gas supply mechanism 50. This control is performed in accordance with a recipe prepared in the control section in advance.
Next, with reference to
Prior to a film-formation step on the wafer W, a pre-coating step is performed, using TiCl4 gas and NH3 gas, to form a thin TiN film on the surface of the worktable 32. Since the pre-coating step is used to form, e.g., a TiN film over the entire surface of the worktable 32, it is performed in a state where no wafer W is present in the process chamber 21.
Specifically, the interior of the process chamber 21 is first vacuum-exhausted by the vacuum-exhaust section 25 with the pressure control valve fully opened. An inactive gas, such as N2 gas, is supplied at a flow rate of, e.g., about 500 sccm from the first and second carrier gas supply sources 53 and 55. The worktable 32 is heated by the heater 34 to a predetermined temperature of, e.g., about 600 to 700° C. N2 gas used as a sheath gas is supplied at a flow rate of, e.g., about 300 sccm from a gas supply mechanism (not shown) into the strut 31 of the worktable 32. The sheath gas is used to set the interior of the strut 31 at a positive pressure, so as to prevent a process gas from coming into the strut 31, in which the lead lines of the heater 34 embedded in the worktable 32 are disposed, thereby preventing corrosion of the lines and terminals in the strut 31. The sheath gas is kept supplied continuously from this time point.
In the step described above, when the temperature inside the process chamber 21 becomes stable, supply of two process gases is turned on at a time point t1, i.e., the first gas supply line 5a starts supplying TiCl4 gas and N2 gas, and the second gas supply line 5b starts supplying NH3 gas. The process chamber 21 is kept vacuum-exhausted, while these process gases are supplied. In order to stabilize the gas flow rate of TiCl4 gas, pre-flow thereof is performed such that it flows not through the process chamber 21 but through the bypass line 5c to the exhaust line, for, e.g. 1 to 60 seconds, such as 10 seconds as in this example, from the time point t1. Then, the valves Va and Vb are switched to change the gas flow passages of the TiCl4 gas, and the gas is supplied into the process chamber 21 until a time point t2, e.g., for 5 to 90 seconds, such as 30 seconds as in this example. On the other hand, the NH3 gas is continuously supplied into the process chamber 21 between the time points t1 and t2, e.g., for 10 to 120 seconds, such as 40 seconds as in this example. Accordingly, the process chamber 21 is supplied with the TiCl4 gas and NH3 gas together, e.g., for 5 to 120 seconds, and preferably 10 to 60 seconds.
As shown in
In this step, the TiCl4 gas and NH3 gas react with each other in accordance with the formula (1) described above, and a TiN film is formed on the surface of the worktable 32. On the other hand, the inner wall of the process chamber 21 and the surface of the showerhead 4 have temperatures lower than the process temperature. Accordingly, the reaction of the formula (1) essentially does not occur on these members, while the two process gases are exhausted in gaseous states therefrom, thereby depositing no TiN film. Then, at the time point t2, the supply of TiCl4 gas and NH3 gas is stopped, and the interior of the process chamber 21 is vacuum-exhausted. During this time, N2 gas, for example, may be supplied.
Then, as shown in
This step cycle between the time points t1 and t3 is repeated a plurality of times, such as 10 cycles or more, and preferably 30 cycles or more. As a consequence, segment films are laminated to form a pre-coat. The number of cycles is suitably adjusted, on the basis of the thickness of a thin film formed by one cycle.
As described above, only the NH3 gas is supplied between the segment film forming steps in the pre-coating process, so that chloride components produced in the segment film forming steps are removed from the process chamber 21. It is thought that chlorine components in the process chamber 21 are removed in accordance with a mechanism, as follows. Specifically, in the reaction of the formula (1), non-reacted TiClx's (x is an arbitrary natural number) are dissociated from TiCl4, and chlorides are produced as byproducts. These substances react with metal portions inside the process chamber and thereby produce metal chlorides. The metal chlorides are reduced by NH3 gas, and HCl produced in this reduction reaction then reacts with NH3, thereby producing ammonium chloride (NH4Cl). Byproducts, such as HCl and NH4Cl, and non-reacted substances, such as TiClx, sublime at the process temperature described above, and are exhausted without being deposited on the inner wall of the process chamber 21 or the like.
In accordance with the steps described above, pre-coating is applied to (by a so-called cycle pre-coating process) over the entire surface of the worktable 32, and a TiN film having a film thickness of, e.g., about 0.7 μm is thereby formed on the worktable 32. Thereafter, the temperature of the worktable 32 is kept at about 400 to 700° C. by the heater 34, and the interior of the process chamber 21 is vacuum-exhausted. With these conditions, the gate valve 26 is opened, and a wafer W is loaded into the process chamber 21 by a transfer arm (not shown). Then, the transfer arm cooperates with the lift pins 36 to place the wafer W onto the top surface (on the pre-coat) of the worktable 32. Then, the gate valve 26 is closed to prepare for a film-formation process (film-formation step) on the wafer W.
In the film-formation step, as shown in
After formation of a TiN film on the surface of the wafer W is completed, the supply of both process gases, TiCl4 and NH3, is stopped, and the interior of the process chamber 21 is purged for, e.g., 10 seconds. Then, NH3 gas is supplied along with N2 gas used as a carrier gas into the process chamber 21 to perform a post-nitride process on the TiN film surface on the wafer W. The same steps described above are repeated to perform the film-formation process for a predetermined number of wafers W.
After a lot of or a predetermined number of wafers W are processed, cleaning is performed to remove unnecessary products deposited inside the process chamber 21. In the cleaning, the temperature of the worktable 32 is set at, e.g., 200° C., and ClF3 gas is supplied into the process chamber 21. By doing so, the pre-coat formed on the surface of the worktable 32 is also removed. Thereafter, when the film-formation step is performed for a predetermined number of other wafers W, the steps starting from the pre-coating step are repeated again, as described above.
According to this embodiment, as will be evident in results described later, it is possible to remarkably reduce metals, which are used for components of the process chamber 21 or showerhead 4, to be taken in a TiN film formed on a wafer W.
According to a conventional pre-coating process, TiCl4 gas and NH3 gas used as process gases are made to flow continuously for a long time. As a consequence, non-reacted TiClx's produced by decomposition of TiCl4, and chlorides, such as HCl and NH4Cl, produced as byproducts are present within the process chamber 21 and in the body of a pre-coat. It is thought that the chlorides react with metal portions inside the process chamber 21 and thereby produce metal chlorides, which are then taken into a film formed on a wafer W during a film-formation step.
In contrast, according to this embodiment, TiCl4 gas and NH3 gas are supplied into the process chamber 21 to form a thin pre-coat (segment film) on the worktable 32, and then NH3 gas is supplied to remove metal chlorides by changing them to gases, such as HCl or NH4Cl. These two steps are combined to form one cycle, which is repeated several tens of times to form a pre-coat having a predetermined film thickness. As a consequence, it is possible to reduce the quantity of metal chlorides produced in the process chamber 21, and to thereby reduce the quantity of metals mixed in a film formed on a wafer W.
In other words, according to this embodiment, a pre-coat is formed not by performing film-formation continuously for a long time, but by repeating film-formation of a segment film and removal of chlorides (purge or exhaust), both of which are steps of short periods of time. As a consequence, it is possible to reduce the quantity of chlorides produced in each step, and to thereby reduce the quantity of chlorides remaining in the process chamber 21.
An experiment was conducted to compare methods according to a conventional technique and the present invention, in terms of the concentration of chlorine present as chlorides in the process chamber 21 when a pre-coating process finished. The results of this experiment revealed that the conventional method showed a chlorine concentration as high as about 2 to 3 at %. On the other hand, this embodiment method showed a reduced chlorine concentration of about 0.1 at %. Accordingly, it has been confirmed that this embodiment can reduce the quantity of metal chlorides produced.
In the pre-coating process, NH3 gas does not have to be intermittently supplied. Furthermore, in the pre-coating process, N2 gas does not have to be supplied from the time point t1 of the embodiment described above.
First, purging is performed with N2 gas until a time point t1 when the temperature in the process chamber 21 becomes stable. At the time point t1, supply of TiCl4 gas and NH3 gas is turned on, and supply of N2 gas is turned off. From the time point t1, only TiCl4 gas is intermittently supplied, while the supply of NH3 gas is maintained, and N2 gas is not supplied. This cycle is repeated a predetermined number of times, e.g., 30 times. Also according to this method, chlorides within the process chamber and in the body of a film are removed by NH3 gas from a time point t2 to a time point t3. Since pre-coating and film-formation processes are repeated, it is possible to attain the same effects as in the case described above.
In the method explained with reference to
As described above, a Ti film can be used for both of the pre-coating of the worktable 32 and film-formation on a wafer W. Accordingly, this embodiment may be applied to, for example, four patterns, i.e., TiN film pre-coating+TiN film formation, Ti film pre-coating+TiN film formation, TiN film pre-coating+Ti film formation, Ti film pre-coating+Ti film formation. In TiN film formation, a Ti film may be formed as an underlying film before a TiN film is formed (including pre-coating).
In any of the cases described above, NH3 gas is used as a reaction gas for removing chlorides, and steps the same as those of the method explained with reference to
In order to confirm effects of this embodiment, an experiment was conducted to compare the conventional method explained in the Background Art and a present example method according to this embodiment. In this experiment, the process temperature was set at 680° C., the process pressure at 40 Pa, the flow rate of TiCl4 gas at about 30 to 50 sccm, the flow rate of NH3 gas at about 400 sccm. In the conventional method, process gases were kept flowing for 10 to 15 minutes to perform a film-formation process on a wafer (an alternative to a pre-coating process). In the present example method, the cycle described above was repeated a plurality of times to perform a film-formation process on a wafer (an alternative to a pre-coating process). In either method, the target film thickness was set at 0.7 μm.
This embodiment may be applied to a case where a thin film other than a Ti or TiN film is formed by a vapor phase reaction, using a metal compound gas that contains a film-formation component metal and a halogen element. For example, it may be applied to a case where a W (tungsten) film is formed, using WF6 (tungsten hexafluoride) gas and H2 gas (SiH4 gas may be used instead). It may be also applied to a case where a WSi2 (tungsten silicide) film is formed, using WF6 gas and SiH2Cl2 (dichlorosilane) gas. It may be also applied to a case where a Ta film is formed, using TaBr3 or TaCl3 gas and H2 gas, or a TaN film is formed, using TaBr3 or TaCl3 gas and NH3 or NH3 and H2 gas.
This embodiment may be also applied to a case where a pre-coat is formed, using an organic metal gas other than a metal compound gas containing a metal and a halogen element. For example, where a Ta2O5 (tantalum oxide) film is formed on a wafer, using PET (pentoethoxytantalum: Ta(OC2H5)5) and O2 gas, a pre-coat is formed, using PET and O2 gas. In this case, non-reacted carbon compounds dissociated from PET and byproducts containing C (carbon) come into the bodies of a process chamber and a thin film (pre-coat film), and then C derived therefrom is taken, although slightly, into the surface of the wafer W during the film-formation process. Accordingly, in the pre-coating process, a cycle including a step of supplying PET and O2 gas together and a step of then supplying only O2 gas is repeated, as in the sequence shown in
In the film-formation apparatus shown in
Since a Ta2O5 film is formed by thermal decomposition reaction of PET, the matching device 46 and RF power supply 47 for plasma generation shown in
In order to heat a target substrate, a conventional lamp heating structure may be employed in place of a resistance heating body built in a worktable. In this case, a worktable is heated by a lamp-heating source disposed below the worktable. Where lamp heating is employed, the worktable is preferably formed of a SiC (silicon carbide) member having a thickness of, e.g., about 7 mm.
Next, an explanation will be given of a film-formation method according to the second embodiment.
In the step S, the worktable is heated to a temperature of 445° C., and N2 gas is supplied through the first gas supply line 5a into the process chamber 21, to perform a pre-coating step. Then, in the step S2, the flow rate of N2 gas is reduced from 1000 sccm to 600 sccm, and O2 gas is supplied into the process chamber 21 at a flow rate of 400 sccm. In the steps S1 and S2, PET gas and N2 gas are supplied through the second supply line 5b for pre-flow, and exhausted not through the process chamber 21 but through the bypass line 5c.
In this case, the PET pre-flow in the step S1 is performed at a flow rate controlled with a flowmeter tolerance of 90 mg±15 (10 to 15) mg. On the other hand, the PET pre-flow in the step S2 is performed at a flow rate controlled with a flowmeter tolerance of 90 mg±5 (3 to 10) mg, so that the PET can be stably supplied into the process chamber. For example, in the step S2, the pre-flow of PET is performed once, for a predetermined time period of 20 seconds or more, and preferably of 30 seconds or more.
Thereafter, in a step S3 (segment film formation step), N2 gas supply through first gas supply line 5a stops, and PET gas and N2 gas flowing through the second gas supply line 5b for pre-flow are switched and supplied into the process chamber 21. As described above, since pre-flow is performed before film-formation, process gases are supplied at stable flow rates from the beginning of the step S3. Furthermore, since the gas flow rate through the process chamber is kept constant 21 (for example, the total flow rate is set at 1000 sccm) from the step S1 to step S3, the temperatures of the worktable 32 and wafer are prevented from varying due to change in the pressure in the process chamber 21.
The film thickness of a deposited segment film (Ta2O5 film) can be adjusted by changing the time period of the step S3, as follows. In this embodiment, where the time period of the step S3 is set at 58 seconds, 71 seconds, 141 seconds, and 281 seconds, the film thickness of a segment film becomes about 5.2 nm, 6.5 nm, 13 nm, and 26 nm, respectively.
In the steps S1 to S3, the interior of the process chamber 21 may be arbitrarily set at a pressure of about 13.3 to 1333 Pa, and preferably of about 39.9 to 667 Pa. The process temperature may be arbitrarily set at a value of about 300 to 800° C., and preferably of about 350 to 500° C.
Then, in a step S4, the supply of PET gas and O2 gas is stopped and only N2 gas is supplied to perform purging. Then, in a step S5, the supply of N2 gas is stopped, i.e., all the gas supplies are stopped, and the interior of the process chamber is vacuum-exhausted. In the step S4, N2 gas is supplied into the process chamber 21 through at least one of the first and second supply lines 5a and 5b and exhausted to perform purging. One pre-coating sequence for the worktable 32 is finished upon the completion of the steps S1 to S5 described above. Afterward, the cycle of steps S1 to S5 or steps S2 to S5 is repeated a necessary number of times. As a consequence, segment films are laminated, thereby forming a pre-coat. The number of repetitions of the cycle is suitably adjusted in accordance with the thickness of a thin film formed by one cycle.
With the process described above, the worktable 32 is covered with a pre-coat of a Ta2O5 film. Thereafter, while a heater 34 maintains the temperature of the worktable 32, the interior of the process chamber 21 is vacuum-exhausted. In this state, a gate valve 26 is opened, and a wafer W is loaded into the process chamber 21 by a transfer arm (not shown). Then, the wafer W is placed on the top surface (on the pre-coat) of the worktable 32 by the transfer arm in cooperation with the lift pins 36. Then, the gate valve 26 is closed to start a film-formation process (film-formation step) on the wafer W.
In the film-formation step, while the interior of the process chamber 21 is vacuum-exhausted, PET and O2 gas are supplied onto the wafer W placed on the worktable 32. By doing so, a Ta2O5 film having a predetermined thickness is formed on the wafer W. This process may employ process conditions the same as those of the step 3 of the pre-coating process.
According to this embodiment, since a film-formation process is performed on a wafer after a pre-coating step, the metal contamination concentration in a thin film formed on the wafer is reduced. An experiment was conducted, as follows: The pre-coating cycle (sequence) shown in
For example, in the data shown by “▴”, where the sequence is repeated 8 times, the pre-coat film thickness formed by each sequence is about 26 nm (210 nm/8). Where the sequence is repeated 16 times, the pre-coat film thickness formed by each sequence is about 13 nm (210 nm/16). Where the sequence is repeated 32 times, the pre-coat film thickness formed by each sequence is about 6.5 nm (210 nm/32).
As shown in
Semiconductor device design rules (pattern line width) become stricter year by year, and require permissible metal contamination (metal contaminant quantity) to be lower. In the current situation, a criterion of the metal contaminant quantity is set at a level of 1.0×1011 (atoms/cm2). Judging from this, the number of repetitions of the pre-coating sequence is preferably set at 13 or more, and preferably at 15 or more. However, a criterion of the metal contaminant quantity may be changed, depending on the user's request. In this respect, as shown in
As described previously, the pre-coat needs to have a certain thickness to prevent the thermal emissivity from varying, thereby maintaining uniformity in film thickness between wafers (inter-surface uniformity). For Ta2O5 films, this certain thickness is about 90 nm. Accordingly, in order to complete a pre-coating process fastest, the thickness of one segment film formed by each pre-coating sequence is set at a value made by dividing 90 nm by the number of repetitions. For example, where the number of repetitions is 4, the segment film thickness is set at about 22.5 nm. Where the number of repetitions is 15, the segment film thickness is set at about 6 nm. However, the thickness of one segment film formed by each pre-coating sequence may be arbitrarily selected.
It is presumed that the following mechanism contributes to the fact that the metal contaminant quantity in a film on a wafer is reduced by repeating the pre-coating sequence a plurality of times. Specifically, a Ta2O5 film is formed by thermal decomposition of PET. O2 gas supplied along with PET is an assist gas, which has some effect on the film quality, reaction rate, and the like of the Ta2O5 film, but does not appear in the chemical reaction formula of production of the Ta2O5 film. This chemical reaction formula is expressed as follows. At first, PET is thermally decomposed, as in formula (11).
2Ta(OC2H5)5→Ta2O5+5C2H4+5C2H5OH (11)
With progress of the thermal decomposition, C2H5OH shown above is decomposed, as in formula (12).
5C2H5OH→5C2H4+5H2O (12)
If metal chlorides, such as FeCl3, are present in the process chamber 21, they react with ethanol shown as an intermediate product in the above formula, and thereby produce ethoxy-compounds, as in formula (13).
FeCl3+3C2H5OH→Fe(OC2H5)3+3HCl (13)
The ethoxy-compounds are readily vaporized by the process temperature in the process chamber 21, and are exhausted. As a consequence, while the pre-coating is performed, it is possible to reduce metal chlorides, which can cause metal contamination during the following film-formation on a wafer. Unlike TiN film pre-coating, Ta2O5 film pre-coating does not bring about metal chlorides during the pre-coating process. On the other hand, the interior of the process chamber 21 is periodically cleaned, using a cleaning gas containing a halogen, such as ClF3 gas. Judging from these facts, it is presumed that the metal chlorides are produced during the cleaning.
Although being vaporized and exhausted, metal ethoxy-compounds are inevitably produced during the pre-coating process, and floats within the process chamber 21 or deposit on the inner wall of the process chamber. Accordingly, as shown in
It happens that there is a vacant period after wafers are sequentially processed and before the next lot starts being processed. This vacant time state can be called idling. Where a process is resumed after idling, the metal contaminant quantity in a film formed on a wafer occasionally increases. As one of the reasons, it is thought that back diffusion of gas, such as alcohol, occurs from the exhaust system into the process chamber 21. Specifically, the exhaust system of the process chamber 21 is provided with a throttle valve for adjusting pressure, a trap for catching non-reacted substances and byproducts, and a vacuum pump, in this order from the upstream side of the exhaust line 24. Although the interior of the process chamber 21 is purged, using an inactive gas, such as N2 gas, during idling, alcohol or the like present in byproducts caught by the trap diffuses back into the process chamber 21. As a consequence, ethoxy-compounds can be produced, as shown in the formula (13).
In consideration of this, where a process is resumed after idling, a pre-coating cycle is performed, as described above, thereby reducing the metal contaminant quantity in a film to be formed on a wafer by the process. In this case, it is also effective to repeat purge and vacuum-exhaust in accordance with the timetable shown in
The step S11 is a Ta2O5 film formation step performed on a wafer immediately before idling. The step S12 is a period of time of the idling (for example, 3,600 seconds, although it varies depending on the situation). In the step S13, O2 gas and N2 gas are supplied into the process chamber 21 to perform first purge, as a preparation to start of the next lot process. Then, in the step S14, N2 gas is supplied into the process chamber 21 at a rate lower than that of the step S13, to perform the second purge. Then, in the step S15, vacuum-exhaust is performed. The step S13 to step S15 are repeated, as needed, i.e., cycle purge is repeated a predetermined number of times. Thereafter, a Ta2O5 film formation process is performed for the next lot of wafers.
In the steps S12 and S14, N2 gas is supplied through at least one of the first and second supply lines 5a and 5b into the process chamber 21 and exhausted to perform purging. In the step S13, the same conditions as those of the film-formation process on a wafer used in the step S11 are used except for PET gas, so that the environment in the process chamber 21 is prepared. Accordingly, this step is also used for conditioning the environment (environment adjustment) in the process chamber 21 to be closer to that for the film-formation process on the next lot of wafers to be performed in succession. The cycle purge shown in
An experiment was conducted to confirm the effect of the cycle purge shown
As described above, the second embodiment is exemplified by a method of forming a tantalum oxide film, using PET as a first process gas (and oxygen as a second process gas). The second embodiment, however, may be applied to a film-formation method that utilizes another organic metal source gas or metal alcoxide, such as a method of forming Ta2O5 film or TEOS-SiO2 film, using Ta(OC2H5)5 or Si(OC2H5)4 as a first process gas, respectively. In these methods, an oxygen-containing gas, such as O2, O3, or H2O, may be used as a second process gas.
As described above, the first and second embodiments reduce the total quantity of contaminants, such as metal, in a film formed on a target substrate after a pre-coating process is performed in the process chamber.
Specifically, in a pre-coating process according to the first and second embodiments, although a first step brings about non-reacted substances dissociated from a process gas and byproducts, which are present within the process chamber or contained in the body of the thin film, a second step exhausts them from the process chamber. As a consequence, it is possible to improve the purity of the composition of a film formed on a target substrate in a subsequent film-formation process.
For example, the second embodiment is explained in an application where a tantalum oxide film is formed, using PET and O2 gas as process gases. In this case, the second step of the pre-coating process is performed, using oxygen gas, which is a reaction gas, as described in the embodiment, thereby removing carbon in the pre-coat and within the process chamber. Where a tantalum oxide film is formed in the process chamber after a long-term idling state, the second step of the pre-coating process is performed by supplying an inactive gas, as described in the embodiment, thereby removing metal compounds within the process chamber.
On the other hand, according to the first embodiment, the first step of the pre-coating process brings about non-reacted halogenated compounds dissociated from a process gas and halogenated compounds produced as byproducts and taken into a film. The second step reduces the halogenated compounds by, e.g., NH3 gas, such that halogenated compounds separated by the reduction reaction are exhausted in a gaseous state from the process chamber. As a consequence, metal contamination less likely occurs in a film formed on a target substrate in a subsequent film-formation step.
For example, where a TiN film is formed, NH3 and TiCl4 can be used as process gases. In this case, TiClx, HCl, and the like produced in the first step are removed from the process chamber in the second step. As a consequence, the quantity of metal chlorides to be taken in a TiN film is reduced in a subsequent film-formation step.
Each of the methods according to the embodiments is performed under the control of the control section 200 (see
Each of the methods according to the embodiments may be written as program instructions for execution on a processor, into a computer readable storage medium or media to be applied to a semiconductor processing apparatus (a film-formation apparatus in this case). Alternately, program instructions of this kind may be transmitted by a communication medium or media and thereby applied to a semiconductor processing apparatus. Examples of the storage medium or media are a magnetic disk (flexible disk, hard disk (a representative of which is a hard disk included in the storage section 212), etc.), an optical disk (CD, DVD, etc.), a magneto-optical disk (MO, etc.), and a semiconductor memory. A computer for controlling the operation of the semiconductor processing apparatus reads program instructions stored in the storage medium or media, and executes them on a processor, thereby performing a corresponding method, as described above.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2002-204138 | Jul 2002 | JP | national |
| 2003-001254 | Jan 2003 | JP | national |
This is a Continuation-in-Part Application of PCT Application No. PCT/JP03/08861, filed Jul. 11, 2003, which was not published under PCT Article 21(2) in English. This application is based upon and claims the benefit of priority from prior Japanese Patent Applications No. 2002-204138, filed Jul. 12, 2002; and No. 2003-001254, filed Jan. 7, 2003, the entire contents of both of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP03/08861 | Jul 2003 | US |
| Child | 11033406 | Jan 2005 | US |
