JP3956049B2 - Method for forming tungsten film - Google Patents

Method for forming tungsten film Download PDF

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Publication number
JP3956049B2
JP3956049B2 JP2003062443A JP2003062443A JP3956049B2 JP 3956049 B2 JP3956049 B2 JP 3956049B2 JP 2003062443 A JP2003062443 A JP 2003062443A JP 2003062443 A JP2003062443 A JP 2003062443A JP 3956049 B2 JP3956049 B2 JP 3956049B2
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tungsten film
gas
tungsten
step
film forming
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JP2004273764A (en
Inventor
耕一 佐藤
正雄 吉岡
成 方
泰隆 溝口
穂高 石塚
健二 鈴木
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東京エレクトロン株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of forming a tungsten film on the surface of an object to be processed such as a semiconductor wafer, and more particularly to an improved invention of the applicant's previous application (Japanese Patent Application No. 2002-234273), in which a passivation tungsten film is formed. The present invention relates to a method for forming a tungsten film with an improved process.
[0002]
[Prior art]
In general, in the manufacturing process of a semiconductor integrated circuit, W (tungsten) or WSi (tungsten) is used to form a wiring pattern on the surface of a semiconductor wafer, which is an object to be processed, or to bury a concave portion between wirings or a concave portion for contact. Silicide), Ti (titanium), TiN (titanium nitride), TiSi (titanium silicide), Cu (copper), Ta2 OFive A thin film is formed by depositing a metal such as (tantalum oxide) or a metal compound. Of the various thin films described above, a tungsten film is frequently used because of its low specific resistance and low film forming temperature. In order to form this type of tungsten film, WF is used as a source gas.6 A tungsten film is deposited by using (tungsten hexafluoride) and reducing it with hydrogen, silane, dichlorosilane or the like.
[0003]
When the tungsten film is formed, a barrier layer in which a Ti film, a TiN film, or a laminated film of both is used as a base film on the wafer surface for the purpose of improving the adhesion and suppressing the reaction with the underlying silicon layer. The tungsten film is deposited on the barrier layer.
Here, when embedding the recesses or the like, hydrogen gas having a lower reducing property than silane is mainly used in order to improve the embedding property. At this time, unreacted WF is used.6 The barrier layer is attacked by the gas, and the barrier layer and fluorine react to expand in volume, thereby generating volcano protruding upward and generating voids in the embedded hole.
[0004]
This will be described with reference to FIG. FIG. 17 is a cross-sectional view showing a buried hole in which a volcano and a void are generated. A buried hole 2 such as a contact hole is formed on the surface of the semiconductor wafer W, and a barrier layer 4 made of, for example, a Ti / TiN film is formed on the surface including the inner surface of the buried hole 2 in advance. And in this state WF6 Gas and H2 When the tungsten film 6 is deposited by supplying gas simultaneously, the WF is buried.6 Fluorine therein diffuses into the barrier layer, and in particular, Ti and fluorine in the barrier layer 4 on the surface react to react with each other, so that the tungsten film 6 is deposited in a protruding shape starting from the vicinity of the buried hole 2 and the tip of the protruding portion Volcano 8 is generated due to the stress of tungsten film 6, and hollow void 10 is generated in buried hole 2.
[0005]
Then, in order to prevent the generation of the Volcano 8 and the like, a nucleation layer of a tungsten film is formed with a slight thickness, for example, about 300 to 500 mm, using silane having a stronger reducing power instead of hydrogen gas first. Then, this nucleation layer is used as the starting point for H2 Gas and WF6 In this case, the surface of the barrier layer 4 as the base film is nucleated by, for example, a surface on which an organic metal film is formed or an oxidized surface. In some cases, the layer was not uniform.
Therefore, prior to the formation of the nucleation layer, the reaction intermediate of silane (SiHx: x <4) is supplied at a low temperature, such as about 400 ° C. ) Is adsorbed on the wafer surface, and the nucleation layer is grown using this as a starting point. FIG. 18 is a diagram showing a process when a buried hole is filled with tungsten using such a method.
[0006]
First, as shown in FIG. 18A, silane (SiH) is applied to a wafer W on which the barrier layer 4 is formed on the entire wafer surface including the inner surface in the embedded hole 2.Four ) Alone, and the SiH is applied to the surface of the wafer W.x An initiation process for attaching the reaction intermediate 12 is performed (FIGS. 18A and 18B). And then, as explained above, WF for a predetermined time6 Gas and SiHFour Gas is simultaneously supplied as shown in FIG. 18C, and a tungsten film is deposited starting from the reaction intermediate 12 to form a nucleation layer 14 (FIG. 18D).
Next, as shown in FIG.6 Gas and H2 By supplying the gas at the same time, a main tungsten film 16 is deposited as shown in FIG.
[0007]
[Problems to be solved by the invention]
Incidentally, the barrier layer 4 formed on the wafer surface may be formed using, for example, a Ti organic compound source. In this case, the carbon component contained in the source gas is taken into the barrier layer 4, and this causes a reaction intermediate of SiHx due to the exposed surface of the barrier layer containing the carbon component even if the above-described initiation treatment is performed. The adhesion of the body is uneven and the nucleation layer 14 is formed unevenly, resulting in poor step coverage of the nucleation layer 14 itself, resulting in poor embedding of the main tungsten film and formation of voids, volcano, etc. There was a problem of being.
Further, when the ratio of the nucleation layer 14 to the total tungsten film including the main tungsten layer 16 is not so large, no problem arises. When the ratio of the thickness of the nucleation layer 14 to the thickness of the nucleation layer becomes so large that it cannot be ignored, voids having a size that cannot be ignored are generated due to the poor step coverage of the nucleation layer 14. There was also a problem such as.
[0008]
The above problems have become particularly serious when the semiconductor manufacturing is further miniaturized and thinned and the inner diameter of the buried hole is, for example, 0.2 μm or less.
The present invention has been devised to pay attention to the above problems and to effectively solve them. The object of the present invention is to improve the throughput and to improve the embedding property, for example, even if the diameter of the embedding hole is small, it is possible to suppress the generation of voids and volcanoes that have an adverse effect on the characteristics, and An object of the present invention is to provide a method for forming a tungsten film with good characteristics.
[0009]
[Means for Solving the Problems]
  The invention defined in claim 1 includes a reducing gas supply step for supplying a reducing gas and a tungsten for supplying a tungsten-containing gas when a tungsten film is formed on the surface of an object to be processed in a processing vessel that can be evacuated. The gas supply process includes a purge process for evacuating while supplying an inert gas between the two processes.And the reducing gas supply process is performed first.An initial tungsten film forming step in which the initial tungsten film is formed by alternately repeating, and a flow rate of the tungsten-containing gas while flowing a reducing gas into the processing vesselIncrease little by littleTo changeLet it flowA passivation tungsten film forming step of forming a passivation tungsten film while gradually increasing the pressure in the processing container, and the reducing gas and the tungsten-containing gas in the processing containerAnd sinkAnd a main tungsten film forming step for forming a main tungsten film.
  As a result, an initial tungsten film as a nucleation layer with high film thickness uniformity was formed, a passivation tungsten film was formed more efficiently, and the main tungsten film was deposited thereafter, so that the embedding characteristics were improved particularly. For example, even when the diameter of the embedding hole is small, generation of voids and volcano that are so large as to adversely affect the characteristics can be suppressed. Further, since the above three series of steps are continuously performed in the same processing container, for example, there is no incubation period generated by changing the processing container, and the throughput can be improved accordingly.
  According to a second aspect of the present invention, there is provided a reducing gas supply step for supplying a reducing gas and a tungsten gas for supplying a tungsten-containing gas when a tungsten film is formed on the surface of an object to be processed in a processing vessel that can be evacuated. An initial tungsten film is formed by interposing a supply process with a purge process for evacuating while supplying an inert gas between the two processes and alternately performing the reducing gas supply process first. The initial tungsten film forming step, and the pressure in the processing vessel is gradually increased by flowing the reducing gas into the processing vessel while changing the flow rate of the tungsten-containing gas little by little. While forming a passivation tungsten film while forming the passivation tungsten film A main tungsten film forming step of forming a main tungsten film by flowing the reducing gas and the tungsten-containing gas, and in the passivation tungsten film forming step, the temperature of the object to be processed is gradually increased. This is a tungsten film forming method.
[0010]
  In this case, for example, billingItem 3As specified, in the passivation tungsten film forming step, the temperature of the object to be processed is gradually increased.
  Also for example, billingIn item 4As defined, between the initial tungsten film forming step, the passivation tungsten film forming step, and the main tungsten film forming step, the temperature of the object to be processed is set.Same degreeTo maintain.
  As described above, by maintaining the process temperature between the respective steps substantially constant, there is no need to raise or lower the process temperature in the middle, so that the throughput can be further improved accordingly.
[0011]
  Also for example, billingItem 5As specified, the pressure in the processing chamber is 2666 Pa (20 Torr) or less in the initial tungsten film forming step and the passivation tungsten film forming step, and is 2666 Pa (20 Torr) or more in the main tungsten film forming step.
[0012]
  Also for example billingItem 6As defined, the tungsten-containing gas is WF6 One of a gas and an organic tungsten source gas.
  Also for example billingItem 7As specified, the reducing gas is H2 Gas, Silane (SiH4 ), Disilane (Si2 H6 ), Dichlorosilane (SiH)2 Cl2 ), Diborane (B2 H6 ), Phosphine (PH3 ).
  Also for example billingItem 8As specified, the tungsten-containing gas is WF.6 The reducing gas is SiH in the initial tungsten film forming step.4 Gas, H in the passivation tungsten film forming step and the main tungsten film forming step.2 Gas.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of a method for forming a tungsten film according to the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a sectional view showing a heat treatment apparatus for performing a tungsten film forming method according to the present invention, FIG. 2 is a view showing a supply mode of each gas, and FIG. 3 is an example of each gas flow rate throughout the film forming process. FIG. 4 is a flowchart showing an example of a tungsten film deposited on the surface of a semiconductor wafer.
First, the heat treatment apparatus for carrying out the method of the present invention will be described. The heat treatment apparatus 20 has, for example, an aluminum treatment vessel 22 having a substantially cylindrical cross section. A shower head portion 24 for selectively introducing, for example, various film forming gases and carrier gases as a flow-controlled processing gas is provided to the ceiling portion in the processing container 22 via a sealing member 26 such as an O-ring. The film forming gas is ejected toward the processing space S from a number of gas ejection ports 28 provided on the lower surface. The shower head portion 24 has a structure in which one or a plurality of diffusion plates 27 having a plurality of diffusion holes 25 are provided to promote the diffusion of the gas introduced therein. It may be used.
[0014]
In the processing container 22, a cylindrical reflector 30 raised from the bottom of the processing container is used as an object to be processed via, for example, three L-shaped holding members 32 (only two are shown in FIG. 1). A mounting table 34 for mounting the semiconductor wafer W is provided.
Below the mounting table 34, a plurality of, for example, three L-shaped lifter pins 36 (only two in the illustrated example) are erected upward, and the base of the lifter pin 36 is A vertically long insertion hole (not shown) formed in the reflector 30 is inserted into the ring member 38 in common. Then, the ring member 38 is moved up and down by a push-up bar 40 penetrating through the bottom of the processing container, so that the lifter pin 36 is inserted into the lifter pin hole 42 penetrating through the mounting table 34 and the wafer W is inserted. It can be lifted.
[0015]
A bellows 44 that can be expanded and contracted is provided in the through hole at the bottom of the container of the push-up bar 40 so as to maintain an airtight state inside the processing container 22, and the lower end of the push-up bar 40 is connected to the actuator 46. .
In addition, an exhaust port 48 is provided at the peripheral edge of the bottom of the processing container 22, and an exhaust passage 50 connected to a vacuum pump (not shown) is connected to the exhaust port 48, and a predetermined amount is passed through the processing container 22. A vacuum can be drawn to a degree of vacuum. Further, a gate valve 52 that is opened and closed when a wafer is carried in and out is provided on the side wall of the processing container 22.
Although not shown, a vacuum gauge (Capamanometer) for measuring pressure is provided in the processing vessel 22, and a pressure control valve (Auto Pressure Control Valve) for adjusting the pressure in the processing vessel 22 is provided in the exhaust passage 50. It has been.
[0016]
In addition, a transmission window 54 made of a heat ray transmission material such as quartz is airtightly provided through a sealing member 56 such as an O-ring at the bottom of the processing vessel directly below the mounting table 34, and below this transmission window A box-shaped heating chamber 58 is provided so as to surround 54. In the heating chamber 58, for example, a plurality of heating lamps 60 are attached as a heating means to a rotating table 62 that also serves as a reflecting mirror. The rotating table 62 is a rotation provided at the bottom of the heating chamber 58 via a rotating shaft. It is rotated by a motor 64. Accordingly, the heat rays emitted from the heating lamp 60 pass through the transmission window 54 and irradiate the lower surface of the thin mounting table 34 to heat it, and further indirectly heat the wafer W on the mounting table 34. To get. By using the heating lamp 60 in this way, the temperature increase rate of the wafer W can be made very fast.
[0017]
Next, the method of the present invention performed using the apparatus configured as described above will be described.
First, the gate valve 52 provided on the side wall of the processing container 22 is opened, the wafer W is loaded into the processing container 22 by a transfer arm (not shown), and the lifter pin 36 is pushed up to deliver the wafer W to the lifter pin 36 side. Then, the lifter pins 36 are lowered by lowering the push-up rod 40, and the wafer W is mounted on the mounting table 34. On the surface of the wafer W, a barrier layer 4 such as a Ti / TiN film has already been formed as a base film in the previous process including the inner surface of the buried hole 2 (see FIG. 18A).
[0018]
Next, a predetermined film forming gas, a carrier gas, or the like is supplied as a processing gas from a processing gas source (not shown) to the shower head unit 24 in a gas supply manner as will be described later, and is supplied to the gas injection holes on the lower surface 28 is supplied almost uniformly into the processing container 22. At the same time, the inside atmosphere is sucked and exhausted from the exhaust port 48 to evacuate the inside of the processing vessel 22 to a predetermined pressure, and the heating lamps 60 of the heating means positioned below the mounting table 34 are rotated. Drives and radiates heat energy.
The radiated heat rays pass through the transmission window 54 and then irradiate the back surface of the mounting table 34 to heat it. Since the mounting table 34 is very thin, for example, about 1 mm as described above, the mounting table 34 is heated quickly. Therefore, the wafer W mounted thereon can be quickly heated to a predetermined temperature. The supplied film forming gas causes a predetermined chemical reaction, and a thin film of tungsten film is deposited on the entire surface of the wafer.
[0019]
In the method of the present invention, the entire film forming process is formed by an initial tungsten film forming step 79, a passivation tungsten film forming step 84, and a main tungsten film forming step 80 as shown in FIG. Here, with reference to FIG. 2, the supply mode of each gas over the whole film-forming process is demonstrated concretely.
FIG. 2 shows three types of gas supply modes. In each mode, for example, Ar and N are used as carrier gases.2 The gas is continuously supplied at a constant flow rate or changing the flow rate as necessary. Similarly, the processing vessel 22 is continuously evacuated during a series of steps.
Here, the tungsten-containing gas is WF.6 Gas and H as the reducing gas2 Gas or this H2 SiH, which has a stronger reducing power than gasFour Gas is used. Further, the initial tungsten film forming process, the passivation tungsten film forming process, and the main tungsten film forming process described below are continuously performed in the same processing vessel 22.
[0020]
First, the gas supply mode of the initial tungsten film forming process shown in FIG. 2A is SiH which is a reducing gas as shown in FIG.Four Reducing gas supply process 70 for supplying gas and WF which is a tungsten-containing gas6 The tungsten gas supply step 72 for supplying the gas is alternately repeated a plurality of times by interposing a purge step 74 for evacuating while supplying a carrier gas as an inert gas between these two steps. An initial tungsten film 76 (see FIG. 4) is formed. That is, SiHFour Gas supply and WF6 The initial tungsten film forming step is performed by alternately repeating the gas supply and interposing the purge step 74 between the repeated steps. Then, the last of the initial tungsten film forming process is completed in the reducing gas supply process 70. The inside of the processing container 22 is formed on the surface of the substrate (wafer) with SiH.Four By attaching SiHx with the gas, a film is easily formed effectively in the next passivation film forming step 84 and the main tungsten film forming step 80. This point is the same in FIGS. 2B to 2C.
[0021]
Once the initial tungsten film 76 has been formed in this way, the next step is to use SiH as the reducing gas.Four H instead of gas2 A passivation tungsten film forming step 84 for forming a passivation tungsten film 82 (see FIG. 4), which is a feature of the present invention, is continuously performed using a gas. Here again, inert gases such as Ar, N2 Gas is continuously flowing. In this passivation tungsten film forming step 84, the same gas type as in the main tungsten film forming step 80, ie, WF6 Gas and H2 Gas, but WF6 H before flowing gas2 The gas is flowed to maintain the flow rate constant, and then the tungsten-containing gas is flowed to change the flow rate gradually. At the same time, the pressure in the processing vessel 22 (process pressure) and the substrate temperature are changed. It is gradually raised (see FIG. 3). The period T5 of the passivation tungsten film forming step 84 is, for example, 3 to 90 seconds, and preferably 10 to 60 seconds. In this case, the pressure in the processing container 22 and the substrate temperature may be kept constant.
[0022]
Specifically, as shown in FIG. 3, after performing a short purge step 74 of the initial tungsten film formation step 79, the WF6 The gas is allowed to flow through the exhaust line without entering the processing vessel 22, and the mass flow meter is stabilized for about 1 to 30 seconds, preferably about 3 to 5 seconds.6 Stabilize the gas flow rate. This WF6 WF after Δt seconds when the gas flow is stable6 WF by flowing gas into the processing vessel 226 Gradually increase the gas flow rate.
H2 Gas supply is WF6 The gas is supplied into the processing container 22 before Δt seconds before the gas flow rate is stabilized. By this passivation tungsten film forming step, a passivation tungsten film is formed on the initial tungsten film.
WF as mentioned above6 The reason for gradually increasing the gas flow rate from a small amount is to form a passivation film that is as thin as possible, so that the WF in the main tungsten film formation process6 This is because the purpose is to suppress damage from gas and reinforce the initial tungsten film of the protective film. Accordingly, the total film formation time can be shortened by shortening the film formation time in the initial tungsten film formation step 79, and the throughput can be improved.
[0023]
In other words, passivation tungsten film formation is H2 Supply the gas supply at a predetermined flow rate, and as described above, WF6 The gas is gradually increased to the supply amount in the main tungsten film forming step 80 over a predetermined time, so that the WF to the underlayer is increased.6 WF to minimize (fluorine) damage6 It is necessary to reduce the gas supply amount. But to get embedding, WF6 The gas needs to be increased. In order to achieve both,2 Supply gas and after a while WF6 The supply of gas is started and the supply amount is gradually increased.
In FIG. 3, the process pressure in the passivation tungsten film forming step 79 is linearly increased from 1000 Pa (7.5 Torr) to 10610 Pa (80 Torr), for example, preferably within a pressure range of 13330 Pa or less, and the process temperature is In a temperature range of 300 ° C. to 450 ° C., for example, preferably linearly increases from 350 to 410 ° C. The treatment time is preferably 10 to 60 seconds, and more preferably 20 to 40 seconds under the conditions of temperature increase and pressure increase. Further, when processing is performed at a constant temperature, the processing time may be 10 to 20 seconds because there is no temperature change of the substrate.
[0024]
Next, when the passivation tungsten film forming step 84 is completed, the WF is left as it is.6 Flow gas flow, H2 The main tungsten film forming step 80 is continuously performed while reducing the gas flow rate and flowing each gas. Here again, an inert gas such as Ar or N is used as a carrier gas.2 Gas is continuously flowing. In this way, the main tungsten film forming step 84 is performed for a predetermined time, and for example, the buried hole 2 is completely filled with the main tungsten film 78. The process pressure and process temperature at this time are not substantially changed from the time when the passivation tungsten film forming step is completed, and are kept constant.
Here, in the initial tungsten film forming step, assuming that the period from one reducing gas supply step 70 to the next reducing gas supply step 70 is one cycle, three cycles are performed in the case of FIG. The number of cycles is not particularly limited.
[0025]
The period T1 of each reducing gas supply step 70 and the period T2 of each tungsten gas supply step 72 are 0.5 to 30 seconds, preferably 1.5 to 10 seconds, respectively, and the period of the purge step 74 T3 is 0 to 30 seconds, preferably 0 to 10 seconds. In the purge step, only vacuuming may be performed. Preferably, the total pressure (total pressure) of the reducing gas, the tungsten-containing gas, and the inert gas is controlled to be constant through the reducing gas supply process 70, the tungsten gas supply process 72, and the purge process 74. This is because, by keeping the total gas pressure constant, the temperature of the wafer (object to be processed) and the adsorption amount of the gas to be coated can be kept constant. The total pressure of the gas is controlled by measuring the pressure in the processing vessel 22 with a vacuum gauge attached to the processing vessel 22 and adjusting the pressure control valve attached to the exhaust passage 50 so that the pressure becomes constant. By doing.
[0026]
Here, since the time of the purge process 74 was evaluated, the result will be described. FIG. 5 shows silane (SiH) in the processing vessel.Four 5A is a diagram showing a distribution state of the partial pressure of FIG. 5A, FIG. 5A shows a case where a diffusion plate 27 is provided in the shower head portion 24, and FIG. The case where no is provided is shown. In the figure, the horizontal axis represents the distance in the radial direction from the wafer center. Here, SiHFour Residual SiH on the wafer when purging for several seconds (0 to 3 seconds) immediately after the supply ofFour The partial pressure is measured.
[0027]
As is clear from FIG. 5, the one where the dispersion plate is provided in the shower head (FIG. 5A) has a low partial pressure in the early stage, and in the case shown in FIG. 5A, approximately 1.5 seconds. SiH by performing a purge process of aboutFour The partial pressure of 1 × 10-1It can be reduced to about Pa, and in the case shown in FIG. 5B, a purge process of about 3 seconds is performed to perform SiH.Four The partial pressure of 1 × 10-1It turns out that it can be reduced to about Pa. Note that the same effect (similar effect as the diffusion plate) can also be obtained by narrowing the gas injection port 28 of the shower head portion.
Therefore, regardless of the structure of the shower head portion, if the purge process is performed for at least about 3 seconds, the partial pressure of residual silane can be made zero and the influence of the gas phase reaction can be ignored.
[0028]
Returning to FIG. 2, the SiH hereFour Gas or WF6 The flow rate of the gas is made relatively small, and the partial pressure ratio thereof is made small. Furthermore, the process temperature is set to a low value, for example, 200 to 500 ° C., preferably 250 to 450 ° C. The initial tungsten film has a thickness of 1 to 50 mm, preferably 3 to 20 mm, in one cycle.
Further, the time of the main tungsten film forming step 80 depends on the film thickness to be formed. Here WF6 Gas flow rate, H2 Both the gas flow rate is increased, the process pressure and the process temperature are slightly increased, and the film formation rate is set large.
[0029]
As a result, the initial tungsten film 76 is deposited relatively uniformly and satisfactorily on the surface of the wafer W. The initial tungsten film 76 functions as the nucleation layer 14 in FIG. 18C, and therefore, the main tungsten film 78 can be deposited on the burying layer with good embeddability.
In the passivation tungsten film forming step 84, which is a feature of the present invention, WF is used.6 Since the passivation tungsten film 82 (see FIG. 4) is formed by changing the gas so as to increase gradually and also increasing the process pressure, the barrier property of the initial tungsten film 76 is reinforced. The initial tungsten film 76 can be made as thin as possible. Furthermore, the effect of reducing the effect of the initial tungsten film 76 having a high resistance can be expected.
For this reason, this passivation tungsten film is a so-called WF.6 It functions as a passivation film or barrier film against the above, and thereby, the WF in forming the main tungsten film6 It is possible to suppress damage to the Ti film due to diffusion of F and further improve the embedding characteristics.
[0030]
That is, the film quality characteristic (barrier property) of the passivation tungsten film 82 is improved, and for example, the diffusion of fluorine atoms to this lower layer can be greatly suppressed.
Furthermore, the initial tungsten film forming step 79, the passivation tungsten film forming step 84, and the main tungsten film forming step 82 can all be performed continuously in the same processing vessel 22, so that the semiconductor wafer can be transferred. Since time can be eliminated and the initial incubation period of the main tungsten film forming step 80 can be eliminated, the throughput can be improved accordingly.
[0031]
Further, the gas supply mode shown in FIG. 2B is the same as the gas supply mode shown in FIG. 2A, in the first reducing gas supply step 70A among the repeated reducing gas supply steps. A parameter formed by the product of the partial pressure (Torr) and the supply time (sec) is set to be larger than the parameter (Torr · sec) of the other reducing gas supply process 70. Here, this SiHFour The parameter (Torr · sec) value is increased by increasing the period T4 of the first reducing gas supply step 70A without changing the gas flow rate, for example, by performing the period of 1 to 120 seconds, preferably 15 to 90 seconds.
[0032]
Thus, the first SiHFour For example, by performing only the gas supply process for a long time, an initiation process is performed on the surface of the wafer W as described above with reference to FIG. Some reaction intermediate will be attached. Accordingly, the initial tungsten film 76 to be deposited thereon is easily grown, abnormal growth is suppressed, and the film can be formed with good film thickness uniformity. Here, each process condition in the gas supply mode of FIG. 2 (B) is demonstrated. In the case shown in FIGS. 2A and 2C, the corresponding parts have the same process conditions.
[0033]
Gas ratio in first reducing gas supply process 70A, SiHFour / Carrier gas = 100 to 1000 sccm / 1000 to 10,000 sccm, process pressure is 20 to 100 Torr (2666-1330 Pa), and process time T4 is 5 to 90 seconds. Regarding the process temperature at this time, the upper limit is 200 to 500 ° C., preferably 250 to 450 ° C. in consideration of avoiding the occurrence of volcano or improving the step coverage.
In addition, SiH at this timeFour The parameter (Torr · sec) of the product of the gas partial pressure and the supply time is 10 to 300 (Torr · sec), preferably 30 to 200 (Torr · sec) in order to avoid the occurrence of volcano.
[0034]
In the initial tungsten formation step, the gas ratio in the second and subsequent reducing gas supply steps 70, SiHFour / Carrier gas = 50 to 500 sccm / 2000 to 12000 sccm, period T1 is 1 to 15 seconds, process pressure is 1 to 20 Torr (133.3 to 2666 Pa), process temperature is 200 to 500 ° C., preferably 250 to 450 ° C. SiHx is deposited under these processing conditions.
Further, the gas ratio in the tungsten gas supply step 72, WF6 / Carrier gas = 5 to 300 sccm / 200 to 12000 sccm, period T2 is 1 to 15 seconds, process pressure is 1 to 20 Torr (133.3 to 2666 Pa), process temperature is 200 to 500 ° C., preferably 250 to 450 ° C. Under this processing condition, a second tungsten film is formed. In this way, the initial tungsten film is formed by alternately repeating the reducing gas supply and the tungsten gas supply process.
[0035]
Here, the reducing gas supply process 70 and the tungsten gas supply process 72 will be described in detail. FIG. 6 shows the relationship between the silane parameter (Torr · sec) at approximately 280 ° C. and the film thickness formed per cycle. In the graph, the film thickness is almost saturated when the parameter is 0.2 or more, whereas when it is smaller than 0.2, the film thickness depends on the size of the parameter, but as a whole the predetermined thickness In order to form the initial tungsten film 76, various parameters can be set by setting the parameters to 0.1 to 10, preferably 0.2 to 5, within a range that stabilizes the film thickness that can be formed in one cycle. The film thickness can be saturated and stabilized within the range of process conditions.
[0036]
FIG. 7 shows WF at about 280 ° C.6 Is a graph showing the relationship between the parameter (Torr · sec) and the film thickness formed per cycle. When the parameter is 0.04 or more, the film thickness is substantially saturated, whereas from 0.04 However, in order to stabilize the film thickness formed in one cycle as described above, the parameter is set to 0.01 to 10, preferably 0.04 to Set to 5.
FIG. 8 is a graph showing the temperature dependence of the film thickness formed per cycle of gas supply. Here, SiHFour And WF6 The film thickness per cycle is shown in the case of alternately supplying 90 times (90 cycles). The horizontal axis represents the actual wafer temperature.
[0037]
As is apparent from this graph, when the wafer temperature is 100 ° C. or lower, the W film is not deposited. From 200 to 300 ° C., the film forming rate of the W film gradually increases with the temperature rise, and thereafter 300 ° C. Then, it turns out that the film-forming speed | velocity | rate increases rapidly with the rise in temperature. Therefore, it can be seen that the wafer temperature (slightly lower than the process temperature) is preferably set to 100 ° C. or higher from the viewpoint of film thickness.
Moreover, FIG. 9 shows WF6 It is the graph which showed the relationship between the parameter (Torr * sec) of gas, and the generation | occurrence | production number of volcano per cell. Here, one cell means an aggregate including about 50,000 contact holes. According to this graph, when the parameter is 0.5 or less, the generation of volcano is zero, but when the parameter is larger than 0.5, the number of generated volcanoes increases approximately proportionally. WF6 The gas parameter is 0.01 to 0.6, preferably 0.04 to 0.5. In this case, the thickness of the initial tungsten film 76 for suppressing the generation of volcano is, for example, about 10 to 200 mm, preferably about 20 to 150 mm, although it depends on the inner diameter of the buried hole 2.
[0038]
Next, in the passivation tungsten film forming step 84, the gas ratio, WF6 / H2 / Carrier gas = 10 to 500 sccm / 500 to 6000 sccm / 2000 to 12000 sccm, the process pressure is changed from 1 Torr (133.3 Pa) to 100 Torr (13330 Pa) as described above, and the process temperature is 200 to 500 ° C. In the case of FIG. 2, it is changed substantially linearly from 350 to 390 ° C., and the process time T5 is 1 to 90 seconds, preferably 3 to 60 seconds. From the top to avoid the generation of volcano, the passivation tungsten film is WF6 It functions as a passivation film or barrier film against the above, and thereby, the WF in forming the main tungsten film6 It is possible to suppress damage to the TiN film due to diffusion of F and further improve the embedding characteristics.
[0039]
The thickness of the passivation tungsten film 82 also depends on the inner diameter of the buried hole 2, but suppresses damage to the base film in the main tungsten film forming process, improves the embedding property, and provides a certain level of step coverage. In order to obtain the above, it should be set within a range of about 10 to 500 mm, preferably about 200 to 400 mm.
In the passivation tungsten film forming step 84, at least one of the process pressure and the process temperature is set to be substantially the same as that in the initial tungsten film forming step in the previous step. Thereby, the transition between both processes can be performed smoothly and in a short time.
[0040]
Further, in the main tungsten film forming process 80, in order to obtain a step coverage and a film forming rate of a certain degree or more while improving the embedding property, the gas ratio, WF6 / H2 / Carrier gas = 50 to 500 sccm / 500 to 6000 sccm / 2000 to 8000 sccm, as described above, the process pressure is 10 to 100 Torr (133.3 to 13330 Pa), the process temperature is 300 to 500 ° C., preferably 350 to 450 ° C. A main tungsten film is formed under these film forming conditions.
[0041]
In the above embodiment, hydrogen and silane were used as the reducing gas, but instead of this, disilane (Si2 H6 ), Dichlorosilane (SiH)2 Cl2 ), Diborane (B2 H6 ), Phosphine (PHThree ) Etc., and these may be combined appropriately. In this case, it is preferable to use a gas having a larger reducing power in the initial tungsten film forming step than in the main tungsten film forming step 80.
Furthermore, the same reducing gas may be used in the initial tungsten film forming step, the passivation tungsten film forming step, and the main tungsten film forming step.
Here, SiH is used in the initial tungsten film forming step.Four Instead of this, H was generated using plasma or using ultraviolet rays.2 A radical (active species) may be used.
As a tungsten-containing gas, WF is used.6 It is not limited to the gas, and an organic tungsten source gas may be used.
[0042]
WF6 Regarding the partial pressure of the gas, the lower limit is about 0.4 Torr (53 Pa) in order to increase the step coverage to some extent, and the upper limit is 2. when the process pressure is 40 Torr or less in order to avoid the occurrence of volcano. It is about 0 Torr (266 Pa). Furthermore, WF6 / H2 The gas ratio is 0.01 to 1, preferably 0.1 to 0.5 in order to increase the step coverage to some extent and avoid volcano. In the main tungsten film forming step 80, WF6 When the process was performed by changing the flow rate of the gas and changing the process pressure, the throughput was improved as the amount of gas was increased. However, the improvement of the throughput was substantially stopped in the vicinity of 70 to 80 Torr. Therefore, the process pressure is preferably about 70 Torr or more.
[0043]
FIG. 10 is a graph showing the temperature dependence of the resistance value of the tungsten film. In the figure, a represents a tungsten film formed by a conventional CVD method (process temperature≈400 ° C.), b represents a tungsten film formed by the method of the present invention at a process temperature of 280 ° C., and c represents tungsten formed by the method of the present invention at a process temperature of 380 ° C. The membrane is shown.
As is apparent from this graph, the films b and c obtained by the method of the present invention have a resistance value that is about 2 to 4 times higher than that of the film a formed by the conventional CVD method. This is presumably because the crystallite size of the films b and c formed by the present method is 2 to 4 times smaller than that of the conventional method. It can also be seen that the films b and c formed by the method of the present invention have a higher resistance value as the film formed at a higher temperature. This is presumably because a film formed at a higher temperature contains a higher concentration of Si.
[0044]
Finally, the evaluation of the F (fluorine) concentration diffused on the wafer surface will be described.
FIG. 11 shows SiH as the reducing gas.Four , Si2 H6 , B2 H6 5 is a graph showing an F concentration (diffusion amount) profile on the wafer surface. Here, the TiN film, the Ti film, and the SiO film are directed downward from the W film (tungsten film).2 A wafer on which films are sequentially formed is used.
As is apparent from this graph, the F concentration in the W film of the method of the present invention is 1 × 10.17Atms / cc, the F concentration in the W film by the conventional CVD method is 3 × 1017Atms / cc, the diffusion amount of F in the W film of the present invention was suppressed to about 1/3, and it was confirmed that this had high barrier properties.
[0045]
<Mode of Transition from Passivation Tungsten Film Formation Process (also referred to as PA Process) to Main Tungsten Film Formation Process (also referred to as MA Process)>
In the method of the present invention described above, the case of “with temperature change” and the case of “without temperature change” (constant temperature) were examined in the passivation tungsten film forming step. The process conditions at this time are as follows.
[With temperature change]
Process temperature: The temperature is raised from 350 ° C. in the PA step to 390 ° C. in the MA step (see FIG. 3).
Process pressure: Increased pressure from 7.5 Torr to 80 Torr.
・ Temperature increase time (pressure increase time): 30 seconds (because a certain amount of time is required for temperature stabilization)
・ WF6 Gas flow rate: Increased from 60 sccm to 350 sccm.
[0046]
[No temperature change]
Process temperature: Maintained constant at 410 ° C. throughout the PA process-MA process.
・ Pressurization time: 15 seconds
・ Process pressure, WF6 The gas flow rate is the same as for “with temperature change”.
The initial tungsten film formation step and other process conditions are set to be the same.
As a result of the above evaluation, in the case of “no temperature change” in which the process temperature was increased and maintained at 410 ° C. in the PA process, the throughput was high and good.
On the other hand, in the case of “with temperature change” in which the process temperature was gradually changed from 350 ° C. to 390 ° C. in the PA process, the embedding characteristics were good contrary to the above.
[0047]
Next, in the initial tungsten film forming step, SiH is used as a reducing gas.Four , Si2 H6 , B2 H6 The case where is used will be described.
Actually, SiH is obtained by using the method of the present invention as shown in FIG.Four , Si2 H6 , B2 H6 The state of void generation in the embedded hole and the evaluation of the embedding characteristics are described below. The inner diameter of the embedding hole at this time was 0.09 μm.
[0048]
The flowchart shown in FIG. 2B is used for the supply mode and process conditions of each gas in the initial tungsten film formation step. The silane, disilane, and diborane gas flow rates were set to be the same.
FIG. 12 shows the temperature dependence of the film formation rate per cycle. It was confirmed that the deposition rate increased with increasing temperature for each gas. It was also found that the film formation starts at a lower temperature in the order of disilane, diborane, and silane, and the film formation rate per cycle increases in the order of disilane, diborane, and silane.
[0049]
Next, FIG. 13 shows the results of examining the film thickness dependence of the specific resistance and surface roughness at a process temperature of 320 ° C. FIG. 13A shows the film thickness dependence of specific resistance, and FIG. 13B shows the film thickness dependence of surface roughness.
It was found that the specific resistance showed a high value in the order of disilane, silane, and diborane. And it was confirmed that the specific resistance is smaller as the film thickness is larger. In particular, disilane has a specific resistance that is drastically smaller than the other two gases.
Further, the surface roughness increases in the order of diborane, silane, and disilane, and the surface roughness increases as the film thickness increases. However, disilane shows a peculiar change, and in the vicinity of the film thickness of 80 mm, a surface-like roughness appears that increases rapidly once and then decreases rapidly.
[0050]
Next, FIG. 14 shows the results of examining the concentrations of F, Si, and B in the film. 14A shows the F concentration, and FIG. 14B shows the Si and B concentrations. In FIG. 14, W represents a tungsten film, and TiN represents an underlying titanium nitride film. Note that the boundary between the two films is actually unclear due to the fusion of both materials, but in the illustrated example, compartments are shown for convenience.
As for the F concentration shown in FIG. 14A, diborane is the smallest amount of F diffused in the TiN film of the underlayer, and it is found that the F concentration has a high barrier property.
As shown in FIG. 14B, the Si and B concentrations in the W film increase in the order of diborane, silane, and disilane, and about 10%, 1%, and 1% or less of B or Si are calculated respectively. Contains. In particular, in the case of diborane, it was found that the amount of B contained in the film was high.
[0051]
Next, FIG. 15 shows the result of examining the crystallinity of tungsten in the film. In this examination, an X-ray diffractometer was used. In the case of disilane, only α-W and β-W cubic tungsten was observed, and it was confirmed that the crystallinity was high.
On the other hand, in the case of silane and diborane, the diffraction lines are broad and the crystallinity is low. In particular, in the case of diborane, it was confirmed that the degree of amorphous state is higher.
[0052]
FIG. 16 shows the result of filling a contact hole with a hole diameter of 0.09 μm and A / R = 12. FIG. 16 is a drawing-substituting photograph showing a buried state of the contact hole.
From FIG. 16, it was confirmed that diborane and silane had good embedding properties, but disilane had voids and the embedding properties were insufficient.
As a result, Si2 H6 In the case of, the characteristics such as a high film forming speed and a large crystallite size are the same as the conventional reducing gas and WF.6 It is the same as the growth mode in which nuclei are formed in the shape of islands as in the case of CVD with simultaneous gas extraction. The decrease in the specific resistance and the decrease in the surface roughness once shown in FIG. 13 are considered to have occurred because the island-shaped nuclei grew and became a continuous film. Since the formed nuclei grow preferentially, the film becomes non-uniform, which causes deterioration of embeddability.
[0053]
On the other hand, B2 H6 In this case, the resistance value is high and the embedding property is the best without seams. This is explained by the inclusion of B at a high concentration of about 10% and, as a result, the crystallite size is small or amorphous is mixed. Since the crystallite size is small, the film is uniform and dense. For this reason, the amount of F diffusion of the base TiN is the smallest and has a high barrier property.
SiHFour In the case of2 H6 And B2 H6 The film growth pattern is B2 H6 As with, the crystallite size is small and the film becomes dense. Even in a contact hole miniaturized with a hole diameter of 0.09 μm and A / R = 12, B2 H6 Therefore, the resistance can be suppressed to a lower level and the adhesion of the film can be secured. Therefore, it is determined from the overall state of voids in the embedded hole and the embedded characteristics, and Si2 H6 , B2 H6 , SiHFour The results were good in the order of. Good contact characteristics can be obtained by using a contact hole diameter of 0.09 μm, which will be effective for the next generation of fine holes of 0.13 μm or less.
In this embodiment, the semiconductor wafer is described as an example of the object to be processed. However, the present invention is not limited to this and can be applied to an LCD substrate, a glass substrate, and the like.
[0054]
【The invention's effect】
  As described above, according to the tungsten film forming method of the present invention, the following excellent operational effects can be exhibited.
  The present inventionAccording to the present invention, an initial tungsten film as a nucleation layer having a high film thickness uniformity is formed, a passivation tungsten film is formed more efficiently, and a main tungsten film is deposited thereafter, so that the embedding characteristic is particularly good. For example, even when the diameter of the embedding hole is small, generation of voids and volcano that are so large as to adversely affect the characteristics can be suppressed. Further, since the above three series of steps are continuously performed in the same processing container, for example, the incubation period generated by changing the processing container is eliminated, and the throughput can be improved correspondingly.
  In particular, in the passivation tungsten film formation process, the pressure is gradually increased while gradually increasing the flow rate of the tungsten-containing gas. At the same time, the barrier property of the initial tungsten film can be reinforced.
Especially in claim 4According to such an invention, by maintaining the process temperature between the steps substantially constant, there is no need to raise or lower the process temperature in the middle, and accordingly, the throughput can be further improved accordingly.
[Brief description of the drawings]
FIG. 1 is a cross-sectional configuration diagram showing a heat treatment apparatus for performing a tungsten film forming method according to the present invention.
FIG. 2 is a diagram showing a supply mode of each gas.
FIG. 3 is a flowchart showing a relationship between an example of each gas flow rate throughout the film forming process and process conditions.
FIG. 4 is an enlarged cross-sectional view showing an example of a tungsten film deposited on the surface of a semiconductor wafer.
FIG. 5 shows silane (SiH in the processing vessel.Four It is a figure which shows the distribution state of the partial pressure of ().
FIG. 6 is a graph showing a relationship between a silane parameter (Torr · sec) and a film thickness formed per cycle.
FIG. 7 WF6 It is a graph which shows the relationship between the parameter (Torr * sec) of this and the film thickness formed per cycle.
FIG. 8 is a graph showing the temperature dependence of the film thickness formed per cycle of gas supply.
FIG. 9 WF6 It is the graph which showed the relationship between the parameter (Torr * sec) of gas, and the generation | occurrence | production number of volcano per cell.
FIG. 10 is a graph showing the temperature dependence of the resistance value of a tungsten film.
FIG. 11 is a graph showing an F concentration (diffusion amount) profile on the wafer surface;
FIG. 12 is a diagram showing the temperature dependence of the film formation rate per cycle.
FIG. 13 is a diagram showing the film thickness dependence of specific resistance and surface roughness at a process temperature of 350 ° C.
FIG. 14 is a diagram showing the concentrations of F, Si, and B in the film.
FIG. 15 is a diagram showing an X-ray diffraction result when the crystallinity of tungsten in the film is examined.
FIG. 16 is a drawing-substituting photograph showing a buried state of a contact hole.
FIG. 17 is a cross-sectional view showing a buried hole in which a volcano and a void are generated.
FIG. 18 is a diagram showing an example of a process for filling a buried hole with tungsten.
[Explanation of symbols]
2 Embedded holes
4 Barrier layer
20 Heat treatment equipment
22 Processing container
24 Shower head
60 Heating lamp
70 Reducing gas supply process
72 Tungsten gas supply process
74 Purge process
76 Initial tungsten film
78 Main tungsten film
79 Initial tungsten film formation process
80 Main tungsten film formation process
82 Passivation tungsten film
84 Passivation tungsten film formation process
W Semiconductor wafer (object to be processed)

Claims (13)

  1. When forming a tungsten film on the surface of the object to be processed in a processing container that can be evacuated,
    A tungsten gas supply step of supplying a reducing gas supply step and the tungsten-containing gas supplied to the reducing gas, the Rutotomoni the reducing gas supplied is interposed a purge step of evacuating while supplying an inert gas between the two steps An initial tungsten film forming process in which the initial tungsten film is formed by alternately repeating the process to be performed first ;
    Passivation tungsten film forming the passivation tungsten film while gradually increasing the pressure in the processing chamber by flowing varied to increase the flow rate of the tungsten-containing gas gradually while flowing a reducing gas into the processing chamber Forming process;
    A main tungsten film forming step of forming a main tungsten film by flowing the reducing gas and the tungsten-containing gas into the processing vessel;
    A tungsten film forming method characterized by comprising:
  2. When forming a tungsten film on the surface of the object to be processed in a processing container that can be evacuated,
      A reducing gas supply step for supplying a reducing gas and a tungsten gas supplying step for supplying a tungsten-containing gas are provided with a purge step for evacuating while supplying an inert gas between the two steps, and the reducing gas supplying step. An initial tungsten film forming step in which an initial tungsten film is formed so as to be alternately repeated so as to be performed first,
      Passivation tungsten film formation for forming a passivation tungsten film while gradually increasing the pressure in the processing vessel by flowing the reducing gas into the processing vessel while gradually changing the flow rate of the tungsten-containing gas. Process,
      A main tungsten film forming step of forming a main tungsten film by flowing the reducing gas and the tungsten-containing gas into the processing vessel,
      The tungsten film forming method, wherein in the passivation tungsten film forming step, the temperature of the object to be processed is gradually increased.
  3.   2. The tungsten film forming method according to claim 1, wherein, in the passivation tungsten film forming step, the temperature of the object to be processed is gradually increased.
  4. And the initial tungsten film forming step, the passivation tungsten film forming process of claim 1, wherein the between the main tungsten film forming step, characterized in that it is maintained at the same the temperature of the object to be processed Tungsten film forming method.
  5. The pressure in the processing vessel is 2666 Pa (20 Torr) or less in the initial tungsten film formation step and the passivation tungsten film formation step, and 2666 Pa (20 Torr) or more in the main tungsten film formation step. tungsten film forming method according to any one of claim 1乃optimum 4.
  6. The tungsten-containing gas, method of forming a tungsten film according to any one of claims 1 to 5, characterized in that any one of the WF 6 gas and organic tungsten source gas.
  7. The reducing gas is any one of H 2 gas, silane (SiH 4 ), disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), diborane (B 2 H 6 ), and phosphine (PH 3 ). method of forming a tungsten film according to any one of claims 1乃optimum 6, characterized by comprising than one.
  8. The tungsten-containing gas is WF 6 gas, the reducing gas is SiH 4 gas in the initial tungsten film forming step, and H 2 gas in the passivation tungsten film forming step and the main tungsten film forming step. method of forming a tungsten film according to any one of claims 1乃optimum 7,.
  9. 9. The method of forming a tungsten film according to claim 1, wherein, in the passivation tungsten film forming step, supply of the reducing gas is started prior to start of supply of the tungsten-containing gas.
  10. The method for forming a tungsten film according to claim 1, wherein the initial tungsten film has a thickness in a range of 10 to 200 mm.
  11. 11. The method of forming a tungsten film according to claim 1, wherein a thickness of the passivation tungsten film is in a range of 10 to 500 mm. 11.
  12. The process temperature of each step is in the range of 200 to 500 ° C. in the initial tungsten film forming step and the passivation tungsten film forming step, and in the range of 300 to 500 ° C. in the main tungsten film forming step. The method for forming a tungsten film according to claim 1, wherein the tungsten film is formed.
  13. 13. The method for forming a tungsten film according to claim 1, wherein in the passivation tungsten film forming step, a process pressure is gradually increased.
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