Abstract:
A semiconductor device manufacturing method comprises a step of forming, by thermal chemical vapor deposition method, silicon nitride films on a plurality of substrates stacked in a reaction tube, with bis tertiary butyl amino silane and NH 3  flowing into the reaction tube accommodating the stacked substrates, wherein the silicon nitride films are formed on the substrates in a state in which a distance “a” between adjacent the substrates and a distance “b” between edges of the substrates and an inner wall of the reaction tube are maintained substantially equal to each other.

Description:
BACKGROUND OF THE INVENTION  
         [0001]    1. Field of the Invention  
           [0002]    The present invention relates to a semiconductor device manufacturing method and a semiconductor manufacturing apparatus, and more particularly, to a semiconductor device manufacturing method including a silicon nitride film manufacturing step using a thermal CVD (Chemical Vapor Deposition) method or a silicon oxynitride film manufacturing step using a thermal CVD method, and to a semiconductor manufacturing apparatus preferably used for the method.  
           [0003]    2. Description of the Related Art  
           [0004]    Conventionally, it is common that a silicon nitride film used in a semiconductor device is formed using mixed gas of SiH 2 Cl 2  (DCS, hereinafter) and NH 3  and that a silicon oxynitride film used in a semiconductor device is formed using mixed gas of DCS, NH 3  and N 2 O.  
           [0005]    According to this method, however, it is necessary to form the silicon nitride film at a temperature as high as 700° C. to 800° C. and as a result, there is a problem that impurities are adversely diffused deeply into a shallow diffused layer and a semiconductor device element can not be formed small in size. Further, there is a problem that NH 4 Cl (ammonium chloride), which is a by-product of reaction, adheres to a discharge port, this NH 4 Cl generates rust on a metal surface, and metal contamination is generated on a semiconductor wafer.  
         SUMMARY OF THE INVENTION  
         [0006]    To solve the problems, the present inventors examined forming a silicon nitride (Si 3 N 4 ) film using NH 3  and SiH 2  (NH(C 4 H 9 )) 2 (bis tertiary butyl amino silane: BTBAS, hereinafter) as raw gases and forming a silicon oxynitride (SiON) film using BTBAS, NH 3  and N 2 O as raw gases. As a result, the inventors have found that the silicon nitride film and the silicon oxynitride film can be formed at a low temperature of about 600° C. and NH 4 Cl, which is a cause of metal contamination, is not generated.  
           [0007]    The present inventors, however, have found that when a silicon nitride film or a silicon oxynitride film is formed using BTBAS, uniformity in thickness of the formed film over the entire surface of the substrate is not sufficient.  
           [0008]    [0008]FIG. 1 shows a structure of a furnace used when a silicon nitride film is formed using BTBAS and NH 3  as raw gases, and when a silicon oxynitride film is formed using BTBAS, NH 3  and N 2 O as raw gases.  
           [0009]    A case in which the silicon nitride film is formed using BTBAS and NH 3  as raw gases will be explained as one example.  
           [0010]    A quartz reaction tube (outer tube)  11  is located outside, and a cylindrical quartz inner tube  12  is disposed inside of the quartz reaction tube  11 . A quartz boat  14  is disposed inside of the quartz inner tube  12 . The quartz boat  14  supports a large number of semiconductor wafers  16 .  
           [0011]    BTBAS and NH 3  are introduced into a furnace through quartz nozzles  21  and  18 , respectively. The gases are first introduced into the quartz inner tube  12  and flows from below upward. The gases are discharged out from the quartz inner tube  12  from above downward.  
           [0012]    BTBAS and NH 3  decomposed by heat during this process forms Si 3 N 4  on the semiconductor wafer  16  and a quartz surface.  
           [0013]    [0013]FIG. 4A shows a schematic transversal sectional view of the quartz inner tube  12  and its interior, and FIG. 4B is a schematic longitudinal sectional view thereof.  
           [0014]    The present inventors first formed a silicon nitride film using BTBAS and NH 3  as raw gases having the same compositions as those used for other raw gases.  
           [0015]    The plurality of semiconductor wafers  16  each having a diameter of 200 mm were stacked by boat columns  25  in the vertical direction in the quartz inner tube  12  having an inner diameter of 260 mm, and films were formed. A distance “b” between edges of the semiconductor wafers  16  and an inner wall of the quartz inner tube  12  was 30 mm. A distance “a” between the adjacent semiconductor wafers  16  was 6.35 mm.  
           [0016]    As a result, a thickness of the Si 3 N 4  film was thin around a peripheral portion of the wafer, and the film at the central portion of the wafer was thin and reentrant in shape. When the silicon oxynitride film was formed using BTBAS, NH 3  and N 2 O as raw gases, the same result was obtained.  
           [0017]    Thereupon, it is a main object of the present invention to provide a semiconductor device manufacturing method and a semiconductor manufacturing apparatus in which when a silicon nitride film is formed using BTBAS and NH 3  as raw gases, and when a silicon oxynitride film is formed using BTBAS, NH 3  and N 2 O as raw gases, the uniformity in thickness of the formed film over the entire surface of the substrate can be enhanced.  
           [0018]    To attain the above object, the present inventors have considered that at the center portion of a semiconductor wafer  16 , because other semiconductor wafers  16  are located below and above the semiconductor wafer, space in the vicinity of the semiconductor wafer is small, but at the peripheral portion of the semiconductor wafer, a large space exists between the semiconductor wafer and the quartz inner tube  12 , and therefore, the film formed on the semiconductor wafer is thick at the peripheral portion of the semiconductor wafer and is thin and reentrant in shape at the central portion of the semiconductor wafer. Following the above-mentioned consideration, the present inventors have studied a relation of relative valves between the distance “a” between the adjacent semiconductor wafers  16  and the distance “b” between the edge of the semiconductor wafer  16  and the quartz inner tube  12 , to distribution of a thickness of a film formed on the semiconductor wafer  16  over the entire surface of the wafer  16 , and as a result, the present inventors have reached the present invention.  
           [0019]    According to a first aspect of the present invention, there is provided a semiconductor device manufacturing method, comprising:  
           [0020]    a step of forming, by thermal chemical vapor deposition method, silicon nitride films on a plurality of substrates stacked in a reaction tube, with bis tertiary butyl amino silane and NH 3  flowing into the reaction tube accommodating the stacked substrates, wherein  
           [0021]    the silicon nitride films are formed on the substrates in a state in which a distance “a” between adjacent the substrates and a distance “b” between edges of the substrates and an inner wall of the reaction tube are maintained substantially equal to each other.  
           [0022]    Preferably, a value of a ratio “b/a”, which is a ratio of the distance “b” between the edges of the substrates and the inner wall of the reaction tube to the distance “a” between the adjacent substrates, is set to be in a range of 0.5 to 1.1, and the films are formed on the substrates in this state.  
           [0023]    Preferably, the substrates are semiconductor wafers, and more preferably, the substrates are semiconductor silicon wafers.  
           [0024]    According to a second aspect of the present invention, there is provided a semiconductor device manufacturing method, comprising:  
           [0025]    a step of forming, by thermal chemical vapor deposition method, silicon oxynitride films on a plurality of substrates stacked in a reaction tube, with bis tertiary butyl amino silane, NH 3  and N 2 O flowing into the reaction tube accommodating the stacked substrates, wherein  
           [0026]    the silicon oxynitride films are formed on the substrates in a state in which a distance “a” between adjacent the substrates and a distance “b” between edges of the substrates and an inner wall of the reaction tube are maintained substantially equal to each other.  
           [0027]    Preferably, a value of a ratio “b/a”, which is a ratio of the distance “b” between the edges of the substrates and the inner wall of the reaction tube to the distance “a” between the adjacent substrates, is set to be in a range of 0.5 to 1.1, and the films are formed on the substrates in this state.  
           [0028]    Preferably, the substrates are semiconductor wafers, and more preferably, the substrates are semiconductor silicon wafers.  
           [0029]    According to a third aspect of the present invention, there is provided a semiconductor manufacturing apparatus, comprising:  
           [0030]    a reaction tube;  
           [0031]    a substrate holder being capable of holding a plurality of substrates in the reaction tube with the plurality of substrates being stacked;  
           [0032]    a gas supply for flowing bis tertiary butyl amino silane and NH 3  into the reaction tube; and  
           [0033]    a heater, wherein  
           [0034]    silicon nitride films are formed on the substrates, by thermal chemical vapor deposition method, in a state in which a distance “a” between adjacent the substrates and a distance “b” between edges of the substrates and an inner wall of the reaction tube are maintained substantially equal to each other.  
           [0035]    Preferably, a value of a ratio “b/a”, which is a ratio of the distance “b” between the edges of the substrates and the inner wall of the reaction tube to the distance “a” between the adjacent substrates, is set to be in a range of 0.5 to 1.1, and the films are formed on the substrates in this state.  
           [0036]    Preferably, the substrates are semiconductor wafers, and more preferably, the substrates are semiconductor silicon wafers.  
           [0037]    According to a fourth aspect of the present invention, there is provided a semiconductor manufacturing apparatus, comprising:  
           [0038]    a reaction tube;  
           [0039]    a substrate holder being capable of holding a plurality of substrates in the reaction tube with the plurality of substrates being stacked;  
           [0040]    a gas supply for flowing bis tertiary butyl amino silane, NH 3  and N 2 O into the reaction tube; and  
           [0041]    a heater, wherein  
           [0042]    silicon oxynitride films are formed on the substrates, by thermal chemical vapor deposition method, in a state in which a distance “a” between adjacent the substrates and a distance “b” between edges of the substrates and an inner wall of the reaction tube are maintained substantially equal to each other.  
           [0043]    Preferably, a value of a ratio “b/a”, which is a ratio of the distance “b” between the edges of the substrates and the inner wall of the reaction tube to the distance “a” between the adjacent substrates, is set to be in a range of 0.5 to 1.1, and the films are formed on the substrates in this state.  
           [0044]    Preferably, the substrates are semiconductor wafers, and more preferably, the substrates are semiconductor silicon wafers. 
       
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0045]    The above and further objects, features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, wherein:  
         [0046]    [0046]FIG. 1 is a schematic sectional view for explaining a vertical-type LPCVD film forming apparatus used in one embodiment of the present invention;  
         [0047]    [0047]FIG. 2 is a schematic view for explaining one example of a BTBAS supply apparatus preferably used in the film forming apparatus used in the one embodiment of the present invention;  
         [0048]    [0048]FIG. 3 is a schematic view for explaining another example of a BTBAS supply apparatus preferably used in the film forming apparatus used in the one embodiment of the present invention;  
         [0049]    [0049]FIGS. 4A and 4B are diagrams for explaining a positional relation between a semiconductor wafer and a quartz inner tube in the vertical-type LPCVD film forming apparatus which uses BTBAS as one of raw gases, wherein FIG. 4A is a schematic transversal sectional view and FIG. 4B is a schematic longitudinal sectional view;  
         [0050]    [0050]FIGS. 5A and 5B are for explaining a relation between a ratio “b/a”, which is a ratio of the distance “b” between the edge of the semiconductor wafer and the inner wall of the reaction tube  12  to the distance “a” between the adjacent semiconductor wafers, and the thickness uniformity of a film over the entire surface of the semiconductor wafer, which film is formed on the semiconductor wafer in the vertical-type LPCVD film forming apparatus which uses BTBAS as one of raw gases, wherein FIG. 5A is a schematic longitudinal sectional view for explaining the distance “a” and the distance “b”, and FIG. 5B is a diagram showing a relation between “b/a” and thickness uniformity of the film over the entire surface of the semiconductor wafer; and  
         [0051]    [0051]FIG. 6 is a transverse sectional view for explaining a preferred positional relation between the inner tube, boat columns and the semiconductor wafers in the vertical-type LPCVD film forming apparatus which uses BTBAS as one of raw gases.  
     
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0052]    Next, one embodiment of the present invention will be explained with reference to the drawings below.  
         [0053]    Since BTBAS used in the present invention is in a liquid state at room temperature, the BTBAS is introduced into a furnace using a BTBAS supply apparatus shown in FIGS. 2 and 3.  
         [0054]    A BTBAS supply apparatus shown in FIG. 2 is a combination of a thermostatic bath and gas flow rate control. A BTBAS supply apparatus shown in FIG. 3 controls a flow rate by a combination of a liquid flow rate control and a vaporizer.  
         [0055]    Referring to FIG. 2, in the BTBAS supply apparatus  4 , an interior of a thermostatic bath  41  containing a BTBAS liquid raw material 42 therein is heated to about 100° C. to increase a vapor pressure of BTBAS, thereby evaporating the BTBAS. Then, the evaporated BTBAS is controlled in flow rate by a mass-flow controller  43 , and supplied, from a BTBAS supply port  44 , to a supply port  22  of a nozzle  21  of an vertical-type LPCVD (low pressure CVD) film forming apparatus shown in FIG. 1. In the BTBAS supply apparatus  4 , pipes from the BTBAS liquid raw material  42  to the BTBAS supply port  44  are covered with pipe heating members  45 .  
         [0056]    Referring to FIG. 3, in the BTBAS supply apparatus  5 , push-out gas of He or N 2  introduced from a push-out gas introducing port  53  is introduced, through a pipe  54 , into a BTBAS tank  51  containing a BTBAS liquid raw material  52  therein, thereby pushing out the BTBAS liquid raw material  52  into a pipe  55 . Then, the BTBAS liquid raw material  52  is controlled in flow rate by a liquid flow-rate control apparatus  56  and sent to a vaporizer  57 . In the vaporizer  57 , the BTBAS liquid raw material  52  is evaporated and supplied, from a BTBAS supply port  58 , to the supply port  22  of the nozzle  21  of the vertical-type LPCVD (low pressure CVD) film forming apparatus shown in FIG. 1. In the BTBAS supply apparatus  5 , pipes from the vaporizer  57  to the BTBAS supply port  58  are covered with pipe heating members  59 .  
         [0057]    Next, the vertical-type LPCVD film forming apparatus which can preferably be used in the present embodiment will be explained with reference to FIG. 1.  
         [0058]    In the vertical-type LPCVD film forming apparatus  1 , a heater  13  is provided outside of a quartz reaction tube  11  so that an interior of the quartz reaction tube  11  can be heated uniformly. A quartz inner tube  12  is provided in the quartz reaction tube  11 . A quartz boat  14  is provided in the quartz inner tube  12 , and a plurality of semiconductor wafers are mounted on the quartz boat  14  and stacked in the vertical direction. The quartz boat  14  is mounted on a cap  15 . The quartz boat  14  is brought into and out from the quartz inner tube  12  by vertically moving the cap  15 . Lower portions of the quartz reaction tube  11  and the quartz inner tube  12  are opened, but they are air-tightly closed by a bottom plate  24  of the cap  15  by moving the cap  15  upward. Apparatus nozzles  18  and  21  are provided in lower portions of the quartz inner tube  12  such as to bring into communication with the quartz inner tube  12 . An upper portion of the quartz inner tube  12  is opened. A discharge port  17  is provided at a lower portion of space between the quartz inner tube  12  and the quartz reaction tube  11  so as to bring into communication with the space. The discharge port  17  is in communication with a vacuum pump (not shown) so as to evacuate the quartz reaction tube  11 . The raw gases supplied from the quartz nozzles  18  and  21  are injected from injection ports  20  and  23  into the quartz inner tube  12 . The gases then move in the quartz inner tube  12  from its lower portion to its upper portion, thereafter downwardly flows through the space between the quartz inner tube  12  and the quartz reaction tube  11 , and is discharged from the discharge port  17 .  
         [0059]    A method for forming a silicon nitride film using the vertical-type LPCVD film forming apparatus  1  will be explained next.  
         [0060]    First, the quartz boat  14  holding a large number of semiconductor wafers  16  is inserted into the quartz inner tube  12  the inside temperature of which is maintained at 600° C. or lower.  
         [0061]    Next, the quartz reaction tube  11  is evacuated from the discharge port  17  to produce a vacuum therein using a vacuum pump (not shown). In order to stabilize a temperature over the entire surface of the wafer, it is preferable to evacuate for about one hour.  
         [0062]    Next, NH 3  gas is charged from a charging port  19  of the quartz nozzle  18  to purge the inside of the quartz reaction tube  11  using NH 3  before BTBAS is charged.  
         [0063]    Then, while NH 3  gas is continuously charged from a charging port  19  of the quartz nozzle  18 , BTBAS is charged from the charging port  22  of the quartz nozzle  21 , and an Si 3 N 4  film is formed on the semiconductor wafer  16 .  
         [0064]    Next, the supply of BTBAS is stopped while keep charging the NH 3  gas from the charging port  19  of the quartz nozzle  18 , thereby purging the quartz reaction tube  11  using NH 3 .  
         [0065]    If only BTBAS is charged, a film different from the Si 3 N 4  film is formed and thus, it is preferable to purge the quartz reaction tube  11  using NH 3  before and after deposition.  
         [0066]    Next, N 2  is allowed to flow into the quartz reaction tube  11  from the quartz nozzle  18  to purge the quartz reaction tube  11  using N 2 , thereby removing NH 3  in the quartz reaction tube  11 .  
         [0067]    Then, the supply of N 2  is stopped and the quartz reaction tube  11  is evacuated to produce a vacuum therein. A set of the purge operation using N 2  and the subsequent evacuation operation in the quartz reaction tube  11  is carried out several times.  
         [0068]    Thereafter, the interior of the quartz reaction tube  11  is brought back from the vacuum state into the atmospheric pressure state. Then, the quartz boat  14  is moved down and taken out from the quartz reaction tube  11 . Then, the quartz boat  14  and the semiconductor wafers  16  are cooled down to room temperature.  
         [0069]    The above is described for forming a silicon nitride film, the above, however, also holds true for forming a silicon oxynitride film except that NH 3  gas and N 2 O gas are charged from the charging port  19  of the quartz nozzle  18 .  
         [0070]    In a situation in which a silicon nitride film is formed using BTBAS and NH 3  as raw gases using the above-described vertical-type LPCVD film forming apparatus  1 , a relation between thickness distribution, over the entire surface of the semiconductor wafer  16 , of a silicon nitride film formed on the semiconductor wafer  16  and a ratio “b/a”, which is a ratio of a distance “b” between an edge of the semiconductor wafer  16  and an inner wall of the quartz inner tube  12  to a distance “a” between the adjacent semiconductor wafers  16  was examined while changing the distance “a” between the adjacent semiconductor wafers  16  without changing the quartz inner tube  12 . A result thereof is shown in FIG. 5B. Conditions under which the data was obtained were that a film formation temperature was 600° C., a pressure was 30 Pa, a flow rate of BTBAS was 85 sccm, and a flow rate of NH 3  was 200 sccm. In this graph, black circles indicate the average value of the thickness uniformities, over each entire surface of the semiconductor wafers, of the films respectively formed on three semiconductor wafers, i.e., top, middle and bottom semiconductor wafers, and vertically extending lines indicate differences between the best and the worst points of film thickness uniformities over each entire surface of the three semiconductor wafers, i.e., top, middle and bottom semiconductor wafers. Here, the top semiconductor wafer means a semiconductor wafer located at 6 to 7% of all the stacked semiconductor wafers from the top, the middle semiconductor wafer means a semiconductor wafer located at middle portion, and the bottom semiconductor wafer means a semiconductor wafer located at 6 to 7% of all the stacked semiconductor wafers from the bottom. Values of the black circles in FIG. 5B are 0.96, 1.10, 1.44, 1.92 and 2.88 from the left.  
         [0071]    It can be found that when “b/a” approaches 1, the film thickness distribution becomes excellent. It is preferable to form a film under a condition that “b/a” is between 0.5 and 1.1. If “b/a” is greater than 1.1, the thickness uniformity of the film over the entire surface of the semiconductor wafer is inferior, or variation in film thickness uniformity among films respectively formed on the top, middle and bottom semiconductor wafers becomes large. If “b/a” is smaller than 0.5, it is difficult to insert the semiconductor wafers into the reaction tube. It is further preferable to form a film under a condition that “b/a” is between 0.96 and 1.10.  
         [0072]    In order to bring “b/a”, close to 1 without changing the quartz inner tube, the distance “a” between the adjacent semiconductor wafers must be increased. If the distance “a” is increased, the number of semiconductor wafers to be processed at one time processing is reduced, and this is not preferable in terms of throughput.  
         [0073]    In order to brig “b/a” close to 1, it is preferable to narrow the distance between the semiconductor wafer  16  and the quartz inner tube  12 .  
         [0074]    Since the distance between the semiconductor wafers  16  is 6.35 mm, 6 to 7 mm is appropriate as the distance between the wafer  16  and the inner tube  12 .  
         [0075]    Therefore, the optimal inner diameter of the quartz inner tube  12  with respect to the wafer  16  having a diameter of 200 mm is 214 mm.  
         [0076]    It can be found that the film thickness distribution when the quartz inner tube  12  is used is within 3% as shown with S in FIG. 5B, and the distribution is improved as compared with 6% in the conventional technique. Since the distance between the semiconductor wafers  16  is not changed, the number of wafers which can be processed at a time is the same as that of the conventional technique.  
         [0077]    As shown in FIG. 6, the boat for supporting the semiconductor wafers  16  is provided with the boat columns  25  which are located at outer side of the wafers  16 . Therefore, the boat can not be inserted into the cylindrical quartz inner tube  12  having the inner diameter of 214 mm. Thus, used is the quartz inner tube  12  provided, at portions corresponding to the boat columns  25 , with boat column grooves  26  which are spaces into which the boat columns  25  are retreated.  
         [0078]    The above-described result was obtained when the silicon nitride film is formed using BTBAS and NH 3  as raw gases, and the almost same result was also obtained when a silicon oxynitride film is formed using BTBAS, NH 3  and N 2 O as raw gases.  
         [0079]    Processing conditions at that time were that a film formation temperature was 595° C., a pressure was 65 Pa, a flow rate of BTBAS was 100 sccm, a flow rate of NH 3  was 400 sccm and a flow rate of N 2 O was 200 sccm.  
         [0080]    According to the present invention, when a silicon nitride film is formed using BTBAS and NH 3  as raw gases, or when a silicon oxynitride film is formed using BTBAS, NH 3  and N 2 O as raw gases, uniformity in thickness of the formed film over the entire surface of the substrate wafer can be enhanced.  
         [0081]    The entire disclosure of Japanese Patent Application No. 2000-37120 filed on Feb. 15, 2000 including specification, claims, drawings and summary are incorporated herein by reference in its entirety.  
         [0082]    Although various exemplary embodiments have been shown and described, the invention is not limited to the embodiments shown. Therefore, the scope of the invention is intended to be limited solely by the scope of the claims that follow.