JP2006210950A - Manufacturing method of semiconductor device, and semiconductor manufacturing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve evenness in the thickness of a film to be deposited on a substrate, when nitride silicon film is deposited by using bis tertial butyl amino silane (BTBAS) and NH<SB>3</SB>as the raw material gases, or when nitride silicon oxide film is formed by using BTBAS, NH<SB>3</SB>and N<SB>2</SB>O as the raw material gases. <P>SOLUTION: When nitride silicon film is deposited on the wafer 16, by making BTBAS and NH<SB>3</SB>flow into the tube 12 accommodated by laminating a plurality of the wafers 16 as the raw material gases with thermal CVD process, or nitride silicon oxide on the wafer 16 by making BTBAS, NH<SB>3</SB>and N<SB>2</SB>O flow into the tube 12 as the raw material gases by thermal CVD process, the value of the ratio b/a of the distance b between the end of a semiconductor wafer 16 and the inner wall of a quartz inner tube 12 to the distance a between the adjacent wafers 16 is made to approximate to 1. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method of manufacturing a semiconductor device and a semiconductor manufacturing device, and more particularly, a method of manufacturing a semiconductor device including a silicon nitride film and a silicon oxynitride film used in the semiconductor device by a thermal CVD (Chemical Vapor Deposition) method. The present invention relates to a method and a semiconductor manufacturing apparatus suitably used in the method.

Conventionally, a silicon nitride film used for a semiconductor device is generally formed by a mixed gas of SiH ₂ Cl ₂ (hereinafter referred to as DCS) and NH ₃ . In addition, a silicon oxynitride film used for a semiconductor device is generally formed using a mixed gas of DCS, NH _3, and N ₂ O.

However, in this method, it is necessary to form a silicon nitride film or a silicon oxynitride film at a high temperature of 700 ° C. to 800 ° C. As a result, impurities in the shallow diffusion layer diffuse deeply due to heat, and the device dimensions are reduced. There is a problem that it cannot be reduced. Further, NH ₄ Cl (ammonium chloride), which is a reaction by-product, adheres to the exhaust port, and this NH ₄ Cl causes rust on the metal surface and causes metal contamination on the semiconductor wafer. .

In order to solve these problems, the present inventors used SiH ₂ (NH (C ₄ H ₉ )) ₂ (Bistal butyl amino silane) and NH ₃ as source gas. and forming a silicon nitride _(Si 3 _{N 4)} film is used as the BTBAS and NH ₃ and _{N 2} O were examined to form a silicon oxynitride film is used as a raw material gas. As a result, it has been found that a silicon nitride film or a silicon oxynitride film can be formed at a low temperature of about 600 ° C., and NH ₄ Cl that causes metal contamination is not generated.

  However, the present inventors have found that in-plane uniformity of the formed film is not sufficient when a silicon nitride film or a silicon oxynitride film is formed using BTBAS.

Furnace configuration used when forming a silicon nitride film using BTBAS and NH ₃ as source gases, or when forming a silicon oxynitride film using BTBAS, NH ₃ and N ₂ O as source gases Is shown in FIG.

A case where a silicon nitride film is formed using BTBAS and NH ₃ as source gases will be described as an example.

  A quartz reaction tube (outer tube) 11 is provided on the outer side, and a cylindrical quartz inner tube 12 is provided on the inner side. Further, a quartz boat 14 is placed inside the quartz inner tube 12, and the quartz boat 14 supports a number of semiconductor wafers 16.

BTBAS and NH ₃ are introduced into the furnace through the quartz nozzles 21 and 18, respectively. The gas is first introduced into the quartz inner tube 12 and flows from the bottom to the top. Then, the air is exhausted from the top to the bottom of the quartz inner tube 12.

BTBAS and NH ₃ thermally decomposed in this process form Si ₃ N ₄ on the semiconductor wafer 16 and the quartz surface.

  Here, FIG. 4A shows a schematic cross-sectional view of the quartz inner tube 12 and the inside thereof, and FIG. 4B shows a schematic vertical cross-sectional view thereof.

The inventors first formed a silicon nitride film using BTBAS and NH ₃ as source gases using a configuration used in another source gas system.

  A plurality of semiconductor wafers 16 having a diameter of 200 mm were stacked in a vertical direction in a quartz inner tube 12 having an inner diameter of 260 mm by boat pillars 25 to form a film. The distance b between the end of the semiconductor wafer 16 and the inner wall of the quartz inner tube 12 is 30 mm. The distance a between adjacent semiconductor wafers was 6.35 mm.

As a result, the Si ₃ N ₄ film became thicker at the periphery of the wafer, and the center portion became a thin slip-like shape. The same was true when a silicon oxynitride film was formed using BTBAS, NH _3, and N ₂ O as source gases.

Accordingly, the main object of the present invention is to form a silicon nitride film using BTBAS and NH ₃ as source gases, or to form a silicon oxynitride film using BTBAS, NH ₃ and N ₂ O as source gases. It is an object of the present invention to provide a film forming method and a film forming apparatus capable of improving the in-plane uniformity of the film thickness of a film to be formed.

  In order to solve the above problems, the inventors have found that the semiconductor wafer 16 has a small space in the vicinity of the semiconductor wafer 16 because the other semiconductor wafer 16 is positioned above and below the central portion of the semiconductor wafer 16. Since there is a large space between the peripheral portion of the wafer and the quartz inner tube 12, the semiconductor is thought to be thick at the peripheral portion of the wafer and thin at the central portion as described above. As a result of diligent research, the present invention reached the present invention as a result of the relationship between the distance a between the wafers 16 and the distance b between the end of the semiconductor wafer 16 and the inner wall of the quartz inner tube 12 and the in-plane distribution of film pressure. did.

That is, according to the present invention,
A step of forming a silicon nitride film on the substrate by a thermal CVD method by supplying bismutual butylamino silane and NH ₃ as source gases into the reaction tube in a reaction tube containing a plurality of substrates stacked and accommodated. A method for manufacturing a semiconductor device comprising:
The silicon nitride film is formed on the substrate with the ratio b / a of the distance b between the edge of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates close to 1. A method for manufacturing a semiconductor device is provided.

Preferably, the reaction tube is purged with NH ₃ before and after the supply of bis (butylbutylaminosilane) into the reaction tube.

Moreover, according to the present invention,
A silicon oxynitride film is formed on the substrate by a thermal CVD method by supplying bis-tert-butylaminosilane, NH ₃ and N ₂ O as source gases into the reaction tube in a reaction tube containing a plurality of stacked substrates. A method of manufacturing a semiconductor device including a step of forming a film,
The silicon oxynitride film is formed on the substrate with the ratio b / a of the distance b between the edge of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates close to 1. A method for manufacturing a semiconductor device is provided.

Preferably, the reaction tube is purged with NH ₃ before and after the supply of bis (butylbutylaminosilane) into the reaction tube.

Moreover, according to the present invention,
A step of forming a silicon nitride film on the substrate by a thermal CVD method by supplying bismutual butylamino silane and NH ₃ as source gases into the reaction tube in a reaction tube containing a plurality of substrates stacked and accommodated. A method for manufacturing a semiconductor device comprising:
There is provided a method for manufacturing a semiconductor device, characterized in that the inside of the reaction tube is purged with NH ₃ before and after the supply of bis (butylbutylaminosilane) into the reaction tube.

Moreover, according to the present invention,
A reaction tube;
A substrate holding means capable of stacking and holding a plurality of substrates in the reaction tube;
Gas supply means for supplying and supplying bis-tert-butylaminosilane and NH ₃ as raw material gases into the reaction tube in the reaction tube;
Heating means,
A silicon nitride film is formed on the substrate by thermal CVD with the ratio b / a of the distance b between the end of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates approaching one. There is provided a semiconductor manufacturing apparatus characterized by forming a film.

Moreover, according to the present invention,
A reaction tube;
A substrate holding means capable of stacking and holding a plurality of substrates in the reaction tube;
Gas supply means for supplying bis-tert-butylamino silane, NH ₃ and N ₂ O as raw material gases into the reaction tube and supplying them into the reaction tube;
Heating means,
A silicon oxynitride film is formed on the substrate by thermal CVD with the ratio b / a of the distance b between the end of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates close to 1. A semiconductor manufacturing apparatus characterized in that is formed into a film is provided.

According to the present invention, and the time of forming the silicon nitride film using the BTBAS and NH ₃ as source gases in forming a silicon oxynitride film using BTBAS and NH ₃ and _{N 2} O as material gas In addition, the in-plane uniformity of the film thickness of the film to be formed can be improved.

  Next, an embodiment of the present invention will be described with reference to the drawings.

  Since BTBAS used in the present invention is a liquid at normal temperature, it is introduced into the furnace using a BTBAS supply apparatus as shown in FIGS.

  The BTBAS supply apparatus shown in FIG. 2 is a combination of a thermostatic bath and gas flow rate control. The BTBAS supply device shown in FIG. 3 performs flow rate control by a combination of liquid flow rate control and a vaporizer.

  Referring to FIG. 2, in the BTBAS supply device 4, the vapor pressure of vaporized BTBAS is increased by heating the inside of the thermostatic chamber 41 provided with the BTBAS liquid raw material 42. The vaporized BTBAS is flow-controlled by the mass flow controller 43 and supplied from the BTBAS supply port 44 to the supply port 22 of the nozzle 21 of the vertical LPCVD (low pressure CVD) film forming apparatus shown in FIG.

  In the BTBAS supply device 4, the pipe from the BTBAS liquid raw material 42 to the BTBAS supply port 44 is covered with a pipe heating member 45.

Referring to FIG. 3, in the BTBAS supply device 5, the extruded gas He or N ₂ introduced from the extruded gas introduction port 53 is introduced into the BTBAS tank 51 including the BTBAS liquid raw material 52 through the pipe 54. Thus, the BTBAS liquid raw material 52 is pushed out to the pipe 55, and then the BTBAS liquid raw material is flow-controlled by the liquid flow rate control device 56 and sent to the vaporizer 57. The vaporizer 57 vaporizes the BTBAS liquid raw material from the BTBAS supply port 58 as shown in FIG. Is supplied to the supply port 22 of the nozzle 21 of the vertical LPCVD (low pressure CVD) film forming apparatus shown in FIG. In this BTBAS supply device 5, the pipe from the vaporizer 57 to the BTBAS supply port 58 is covered with a pipe heating member 59.

  Next, a vertical LPCVD film forming apparatus that can be suitably used in this embodiment will be described with reference to FIG.

  The vertical LPCVD film forming apparatus 1 includes a heater 13 outside the quartz reaction tube 11 so that the inside of the quartz reaction tube 11 can be heated uniformly. A cylindrical quartz inner tube 12 is provided in the quartz reaction tube 11. In the quartz inner tube 12, there is provided a quartz boat 14 on which a plurality of semiconductor wafers are stacked in the vertical direction. The quartz boat 14 is mounted on a cap 15, and is inserted into the quartz inner tube 12 and taken out from the quartz inner tube 12 by moving the cap 15 up and down. The lower part of the quartz reaction tube 11 and the quartz inner tube 12 has an open structure, but when the cap 15 is lifted, it is closed by the bottom plate 24 of the cap 15 and has an airtight structure. Quartz nozzles 18 and 21 are provided in communication with the lower part of the quartz inner tube 12. The upper part of the quartz inner tube 12 is open. In the lower part of the space between the quartz inner tube 12 and the quartz reaction tube 11, an exhaust port 17 is provided in communication. The exhaust port 17 communicates with a vacuum pump (not shown), and the inside of the quartz reaction tube 11 can be depressurized. The source gases supplied from the quartz nozzles 18 and 21 are ejected from the respective ejection ports 20 and 23 into the quartz inner tube 12, and then move from the lower part to the upper part in the quartz inner tube 12. It flows downward through the space between the quartz reaction tube 11 and is exhausted from the exhaust port 17.

  Next, a method for manufacturing a silicon nitride film using the vertical LPCVD film forming apparatus 1 will be described.

  First, the quartz boat 14 holding a large number of semiconductor wafers 16 is inserted into the quartz inner tube 12 maintained at a temperature of 600 ° C. or lower.

  Next, vacuum exhaust is performed from the exhaust port 17 using a vacuum pump (not shown). In order to obtain an in-plane temperature stabilization effect of the wafer, it is preferable to evacuate for about 1 hour.

Next, NH ₃ gas is injected from the injection port 19 of the quartz nozzle 18, and the inside of the quartz reaction tube 11 is purged with NH ₃ before flowing BTBAS.

Next, NH ₃ gas is continuously injected from the injection port 19 of the quartz nozzle 18, and BTBAS is injected from the injection port 22 of the quartz nozzle 21 to form a Si ₃ N ₄ film on the semiconductor wafer 16.

Next, while the NH ₃ gas is being injected from the inlet 19 of the quartz nozzle 18, the BTBAS supply is stopped and the quartz reaction tube 11 is purged with NH ₃ .

When only BTBAS is flowed, a film different from the Si ₃ N ₄ film is formed. Therefore, it is preferable to purge with NH ₃ before and after deposition.

Next, N ₂ is caused to flow into the quartz reaction tube 11 from the quartz nozzle 18 and N ₂ purge is performed to remove NH ₃ in the quartz reaction tube 11.

Thereafter, the supply of N ₂ is stopped and the quartz reaction tube 11 is evacuated. N ₂ purge and subsequent vacuum evacuation in the quartz reaction tube 11 are performed several times as a set.

  Thereafter, the inside of the quartz reaction tube 11 is returned from the vacuum state to the atmospheric pressure state, and then the quartz boat 14 is lowered and pulled out from the quartz reaction tube 11, and then the quartz boat 14 and the semiconductor wafer 16 are lowered to room temperature.

The above is the case where a silicon nitride film is formed. However, when a silicon oxynitride film is formed, the NH ₃ gas and the N ₂ O gas are allowed to flow from the inlet 19 of the quartz nozzle 18. The other points are the same.

In the case where a silicon nitride film is formed by using the above-described vertical LPCVD film forming apparatus 1 and BTBAS and NH ₃ as raw material gases by the above method, first, a semiconductor wafer without changing the quartz inner tube 12 is used. By changing the distance a between the semiconductor wafers 16, the ratio b / a between the distance b between the end of the semiconductor wafer 16 and the inner wall of the quartz inner tube 12 and the distance a between the adjacent semiconductor wafers 16 is increased on the semiconductor wafer 16. The relationship between the in-plane distribution of the thickness of the silicon nitride film formed on the substrate was investigated. The result is shown in FIG. 5B. The conditions for obtaining this data were a film forming temperature of 600 ° C., a pressure of 30 Pa, a BTBAS flow rate of 85 sccm, and a NH ₃ flow rate of 200 sccm. In this graph, the black circles represent the average in-plane uniformity of the three semiconductor wafers, that is, the top, center, and bottom semiconductor wafers, and the lines extending vertically indicate the three semiconductor wafers, that is, the top and center. This represents the difference between the best and bad in-plane uniformity of the semiconductor wafer at the bottom and bottom. Here, the top means a semiconductor wafer in a position of 6 to 7% from the top of all the laminated semiconductor wafers, the center means a semiconductor wafer in the center, and the bottom. Means a semiconductor wafer located 6 to 7% from the bottom. The values of b / a for each black circle in FIG. 5B are 0.96, 1.10, 1.44, 1.92, and 2.88, respectively, from the left.

  It can be seen that the film thickness distribution is improved when b / a approaches 1. It is preferable to form the film under conditions such that b / a takes a value between 0.5 and 1.1. If b / a is greater than 1.1, in-plane uniformity is poor, or variation in in-plane uniformity among the semiconductor wafers at the top, center, and bottom becomes large. This is because it becomes difficult to insert the gas into the reaction tube. Further, it is more preferable to perform film formation under a condition where b / a takes a value between 0.96 and 1.10.

  In order to make b / a close to 1 without changing the quartz inner tube, the distance a between adjacent semiconductor wafers must be increased, and as a result, the number of processed semiconductor wafers per process decreases. The throughput is not good.

  Therefore, in order to make b / a close to 1, it is preferable to reduce the distance between the semiconductor wafer 16 and the quartz inner tube 12.

  Since the distance between the semiconductor wafers 16 is 6.35 mm, the distance between the wafer 16 and the inner tube 12 may be 6 to 7 mm.

  Therefore, for the wafer 16 having a diameter of 200 mm, the inner diameter of the quartz inner tube 12 is optimally 214 mm.

  It can be seen that the film thickness distribution when this quartz inner tube 12 is used is improved within 3% compared with the conventional 6% as indicated by S in FIG. 6B. Further, since the distance between the semiconductor wafers 16 is not changed, the number of processed wafers is the same as the conventional one.

  As shown in FIG. 6, the boat supporting the semiconductor wafer 16 has a boat column 25, and the boat column 25 is positioned outside the wafer 16, so that the boat is mounted on the cylindrical quartz inner tube 12 having an inner diameter of 214 mm. It cannot be inserted. Therefore, the quartz inner tube 12 provided with a boat column groove 26 corresponding to the boat column 25, which is a space for evacuating the boat column 25, is used.

If above, although the case of forming a silicon nitride film using the BTBAS and NH ₃ as source gases for forming a silicon oxynitride film using BTBAS and NH ₃ and _{N 2} O as material gas About the same result was obtained.
The processing conditions at this time were a film forming temperature of 595 ° C., a pressure of 65 Pa, a BTBAS flow rate of 100 sccm, an NH ₃ flow rate of 400 sccm, and an N ₂ O flow rate of 200 sccm.

It is a schematic sectional drawing for demonstrating the vertical LPCVD film-forming apparatus used by one embodiment of this invention. It is the schematic for demonstrating the BTBAS supply apparatus used suitably in the film-forming apparatus used by one embodiment of this invention. It is the schematic for demonstrating the BTBAS supply apparatus used suitably in the film-forming apparatus used by one embodiment of this invention. FIG. 4A is a schematic cross-sectional view and FIG. 4B is a schematic cross-sectional view for explaining the positional relationship between a semiconductor wafer and a quartz inner tube in a vertical LPCVD film forming apparatus using BTBAS as one of source gases. It is a longitudinal cross-sectional view. The ratio b / a between the distance b between the end of the semiconductor wafer and the quartz inner tube 12 and the distance a between the semiconductor wafers in the vertical LPCVD film forming apparatus using BTBAS as one of the source gases, and the semiconductor wafer It is a figure for demonstrating the relationship with the wafer surface uniformity of the film | membrane formed on the top, FIG. 5A is a schematic longitudinal cross-sectional view for demonstrating the distance a and the distance b, FIG. It is a figure which shows the relationship with wafer in-plane uniformity. In the vertical LPCVD film forming apparatus using BTBAS as one of the source gases, it is a cross-sectional view for explaining a preferred positional relationship among the inner tube, the boat column, and the semiconductor wafer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Vertical-type film-forming apparatus 4, 5 ... BTBAS supply apparatus 11 ... Quartz reaction tube 12 ... Quartz inner tube 13 ... Heater 14 ... Quartz boat 15 ... Cap 16 ... Semiconductor wafer 17 ... Exhaust port 18, 21 ... Quartz nozzle 25 ... Boat column 26 ... Boat column groove 41 ... Constant temperature bath 51 ... BTBAS raw material tank 42, 52 ... BTBAS liquid raw material 53 ... Extruded gas inlet 54, 55 ... Piping 43 ... Mass flow controller 44, 58 ... BTBAS supply port 56 ... Liquid flow rate control Apparatus 57 ... Vaporizer 45, 59 ... Pipe heating member

Claims (6)

A step of forming a silicon nitride film on the substrate by a thermal CVD method by supplying bismutual butylamino silane and NH ₃ as source gases into the reaction tube in a reaction tube containing a plurality of substrates stacked and accommodated. A method for manufacturing a semiconductor device comprising:
The silicon nitride film is formed on the substrate with the ratio b / a of the distance b between the edge of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates close to 1. A method for manufacturing a semiconductor device. A silicon oxynitride film is formed on the substrate by a thermal CVD method by supplying bis-tert-butylaminosilane, NH ₃ and N ₂ O as source gases into the reaction tube in a reaction tube containing a plurality of stacked substrates. A method of manufacturing a semiconductor device including a step of forming a film,
The silicon oxynitride film is formed on the substrate with the ratio b / a of the distance b between the edge of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates close to 1. A method of manufacturing a semiconductor device. _{3. The} method of manufacturing a semiconductor device according to claim 1, wherein the reaction tube is purged with NH ₃ before and after the supply of bis (butylbutylaminosilane) into the reaction tube. A step of forming a silicon nitride film on the substrate by a thermal CVD method by supplying bismutual butylamino silane and NH ₃ as source gases into the reaction tube in a reaction tube containing a plurality of substrates stacked and accommodated. A method for manufacturing a semiconductor device comprising:
A method of manufacturing a semiconductor device, comprising purging the inside of the reaction tube with NH ₃ before and after stopping the supply of bis (butylbutylaminosilane) into the reaction tube. A reaction tube;
A substrate holding means capable of stacking and holding a plurality of substrates in the reaction tube;
Gas supply means for supplying and supplying bis-tert-butylaminosilane and NH ₃ as raw material gases into the reaction tube in the reaction tube;
Heating means,
A silicon nitride film is formed on the substrate by thermal CVD with the ratio b / a of the distance b between the end of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates approaching one. A semiconductor manufacturing apparatus characterized in that a film is formed. A reaction tube;
A substrate holding means capable of stacking and holding a plurality of substrates in the reaction tube;
Gas supply means for supplying bis-tert-butylamino silane, NH ₃ and N ₂ O as raw material gases into the reaction tube and supplying them into the reaction tube;
Heating means,
A silicon oxynitride film is formed on the substrate by thermal CVD with the ratio b / a of the distance b between the end of the substrate and the inner wall of the reaction tube and the distance a between the adjacent substrates close to 1. A semiconductor manufacturing apparatus characterized in that a film is formed.

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