The film forming system in accordance with this invention comprises a chamber, a precursory gas supplying line that supplies the chamber with precursory gas, a reactive gas supplying line that supplies the chamber with reactive gas, and a purge gas supplying line that supplies purge gas that purges the precursory gas and the reactive gas, and forms a thin film on a substrate of semiconductor in the chamber by supplying precursory gas or reactive gas and conducting purge alternately.
A precursory gas middle line 22 as a middle line having a certain volume is arranged on a part of the precursory gas supplying line and a reactive gas middle line 12 as a middle line having ascertain volume is arranged on a part of the reactive gas supplying line.
An example of conducting film forming is shown; an Al2O3 film as a thin film is deposited on a substrate 82 of Si with TMA (trimethyl aluminum) Al(CH3)3 used as the precursory gas and H,O used as the reactive gas. Ar gas is used as the purge gas and carrier gas.
A schematic diagram of the system is shown in
The film forming system comprises three mass flow controllers (abbreviated as MFC) m1, m2, m3 to send out Ar gas as the carrier gas and the purge gas, a reactive gas tank 6 to store H2O as being the reactive gas 62, a precursory gas tank 7 to store TMA as being the precursory gas 72, a chamber 8 to form the thin film and a pump 9 to suck each gas and to keep the inside of the chamber 8 depressurized.
Each component will be described in detail.
The MFC m1, m2, m3 controls a flow rate of the carrier gas or the purge gas. The MFC m1 is set to send out the carrier gas or the purge gas at about 180 ml/min, the MFC m2 at about 60 ml/min, and the MFC m3 at about 200 ml/min.
The reactive gas tank 6 is arranged to keep H2O at about 25° C. by the use of a constant temperature water tank for reactive gas 61 and to output the reactive gas (H2O) by receiving the carrier gas.
The precursory gas tank 7 is arranged to keep TMA at about 20° C. by the use of a constant temperature water tank for precursory gas 71 and to output the precursory gas (TMA) by receiving the carrier gas.
The chamber 8 is kept in a depressurized state of about 10˜0.1 Torr and comprises a heater 81 that conducts resistance heating. The heater 81 is set to make the surface temperature of the substrate 82 of Si placed on the heater 81 at 250˜300° C.
The pump 9 is both for sucking each gas and for keeping the inside of the chamber 8 depressurized.
The line between each part will be explained as follows.
The MFC m1 is connected to the reactive gas tank 6 through a carrier gas supplying line for reactive gas a and the reactive gas tank 6 is connected to the chamber 8 through a reactive gas supplying line 1.
The MFC m2 is connected to the precursory gas tank 7 through a carrier gas supplying line for precursory gas b and the precursory gas tank 7 is connected to the chamber 8 through a precursory gas supplying line 2.
Each of the reactive gas supplying line 1 and the precursory gas supplying line 2 is a line that is independently arranged each other and a flow path for each gas is independent. Then the gas flowing inside each line 1, 2 is not mixed in the line 1, 2.
The chamber 8 is connected to the pump 9 through an exhaust line 5.
An inlet of a purge gas supplying line 3 is mounted on the MFC m3, an outlet of a bypath line 4 (bypath line) is mounted on the pump 9, and an outlet of the purge gas supplying line 3 and an inlet of the bypath line 4 are connected through a switching valve 3b that can make an open and close movement.
Next, each line will be explained for detail with explaining connection of each line.
Two three-way valves 1b1, 1b2 each of which furcates in three directions are arranged on a flow path of the reactive gas supplying line 1 and the reactive gas middle line 12 is formed between the three-way valves 1b1 and 1b2 by dividing the reactive gas supplying line 1 by the use of a pair of the three-way valves 1b1, 1b2. A volume of the reactive gas middle line 12 is about 15 ml.
The reactive gas supplying line 1 comprises a reactive gas middle line input part 11 that inputs the reactive gas to the reactive gas middle line 12, the reactive gas middle line 12 to which the reactive gas can be filled, and a reactive gas middle line output part 13 that outputs the reactive gas to the chamber 8.
The three-way valve can determine a direction to which the gas is sent by closing an arbitrary port among three ports. The three-way valve 8 used in this embodiment is a three-way magnetic valve driven by electromagnetic force, however, it may be of an air driven type.
The three-way valve (the reactive gas middle line inlet valve) 1b1 arranged at an inlet of the reactive gas middle line 12 is connected to the reactive gas middle line input part 11, the reactive gas middle line 12 and a purge gas supplying branch line for reactive gas 3p1 that connects between lines, and the purge gas supplying branch line for reactive gas 3p1 is connected to the purge gas supplying line 3.
The three-way valve (the reactive gas middle line outlet valve) 1b2 arranged at an outlet of the reactive gas middle line 12 is connected to the reactive gas middle line 12, the reactive gas middle line output part 13 and a bypath branch line for reactive gas 4p1 that connects between lines, and the bypath branch line for reactive gas 4p1 is connected to the bypath line 4.
Two three-way valves 2b1, 2b2 each of which furcates in three directions are arranged on a flow path of the precursory gas supplying line 2 and the precursory gas middle line 22 is formed between the three-way valves 2b1 and 2b2 by dividing the precursory gas supplying line 2 by the use of a pair of the three-way valves 2b1, 2b2. A volume of the precursory gas middle line 22 is about 5 ml.
The precursory gas supplying line 2 comprises a precursory gas middle line input part 21 that input the precursory gas to the precursory gas middle line 22, the precursory gas middle line 22 to which the precursory gas can be filled, and a precursory gas middle line output part 23 that outputs the precursory gas to the chamber 8.
The three-way valve (the precursory gas middle line inlet valve) 2b1 arranged at an inlet of the precursory gas middle line 22 is connected to the precursory gas middle line input part 21, the precursory gas middle line 22 and a purge gas supplying branch line for precursory gas 3p2 that connects between lines, and the purge gas supplying branch line for precursory gas 3p2 is connected to the purge gas supplying line 3.
The three-way valve (the precursory gas middle line outlet valve) 2b2 arranged at an outlet of the precursory gas middle line 22 is connected to the precursory gas middle line 22, the precursory gas middle line output part 23 and a bypath branch line for precursory gas 4p2 that connects between lines, and the bypath branch line for precursory gas 4p2 is connected to the bypath line 4.
Followings are an outline of the behavior of the film forming system.
The precursory gas (TMA) and the reactive gas (H2O) are vaporized by a method such as a bubbling method and supplied to the chamber 8 by the carrier gas through the precursory gas supplying line 2 and the reactive gas supplying line 1 respectively.
A device to supply the gas will be explained including movements of each valve.
An enlarged view of the valve is shown in
The switching valve 3b is open and the purge gas is sent out to the bypath line 4. The reactive gas middle line inlet valve 1b1 closes a port at a side of the purge gas supplying branch line for reactive gas 3p1 so as to send out the reactive gas to the reactive gas middle line 12. The reactive gas middle line outlet valve 1b2 closes a port at a side of the reactive gas middle line output part 13 so as to send out the reactive gas to the bypath line 4 through the bypath branch line for reactive gas 4p1. The precursory gas middle line inlet valve 2b1 closes a port at a side of the purge gas supplying branch line for precursory gas 3p2 so as to send out the precursory gas to the precursory gas middle line 22. The precursory gas middle line outlet valve 2b2 closes a port at a side of the precursory gas middle line output part 23 so as to send out the precursory gas to the bypath line 4 through the bypath branch line for precursory gas 4p2. The direction to which the gas is sent out from each valve 1b1, 1b2, 2b1, 2b2 is shown by an arrow in
First, the precursory gas (TMA) is supplied in initiating a process of film forming.
The precursory gas is sent out to the precursory gas middle line output part 23 by closing the port locating at a side of the bypath branch line for precursory gas 4p2 of the precursory gas middle line outlet valve 2b2 so as to be in a state shown in
Then the precursory gas is deposited on the substrate and purged.
The purge gas is sent out to the precursory gas middle line 22 by closing the switching valve 3b and a port locating at a side of the precursory gas middle line input part 21 of the precursory gas middle line outlet valve 2b1 so as to be in a state shown in
The reactive gas is filled in the reactive gas middle line 12 during a period from the initiation of supplying the precursory gas (TMA) to the completion of purging the inside of the chamber 8.
Next, the reactive gas (H2O) is supplied.
The switching valve 3b is open and the purge gas is sent out to the bypath line 4, a port at a side of the purge gas supplying branch line for precursory gas 3p2 of the precursory gas middle line inlet valve 2b1 is closed and the precursory gas is sent out to the precursory gas middle line 22, a port at a side of the precursory gas middle line output part 23 of the precursory gas middle line outlet valve 2b2 is closed and the precursory gas is sent out to the bypath branch line for precursory gas 4p2, and a port at a side of the bypath branch line for reactive gas 4p1 of the reactive gas middle line outlet valve 1b2 is closed and the reactive gas is sent out to the reactive gas middle line output part 13 so as to be in a state shown in
Next, a thin film is formed by the reactive gas and then the reactive gas is purged.
The purge gas is sent out to the reactive gas middle line 12 by closing the switching valve 3b and a port locating at a side of the reactive gas middle line input part 11 of the reactive gas middle line inlet valve 1b1 so as to be in a state shown in
The precursory gas is filled in the precursory gas middle line 22 during a period from the initiation of supplying the reactive gas (H2O) to the completion of purging the inside of the chamber 8.
A single cycle of supplying the precursory gas (TMA) and the reactive gas (H2O) will be completed with the above process. Then the above process from the state shown in
An image of a change over time of the gas supplied to the chamber 8 is shown in
In this embodiment shown in
In addition, comparison was made for three cases concerning the performance in this embodiment: with a length of the precursory gas middle line output part 23 from the precursory gas middle line outlet valve 2b2 to the chamber 8 set to be 100 mm and with an inside diameter of the precursory gas middle line output part 23 set to be 3.1 mm, 6.3 mm, and 9.4 mm.
Each inside volume of the precursory gas middle line output part 23 is 754 mm3, 3116 mm3 and 6936 mm3 respectively. Since the flow rate of the purge gas is 200 ml/min, it can be calculated 0.2 second, 0.93 second and 2.1 second to replace the inside of the precursory gas middle line output part 23. This period is short in comparison with the purge period of 5 second determined in this embodiment. If the gas replacement of the inside of the precursory gas middle line output part 23 is insufficient when the reactive gas is supplied to the chamber 8, the precursory gas is exposed to the reactive gas (H2O). As a result, particles (fine particles of aluminum oxide) are generated inside the precursory gas middle line output part 23 and the surface of the substrate is contaminated.
A number of particles that attach to a wafer is shown in
Generally, the period to flow the purge gas is elongated in order to avoid this problem. However, it will elongate the period required for film forming, thereby failing improvement of the throughput.
Consequently, in order to make it possible to purge the inside of the precursory gas middle line output part 23 by the use of the purge gas quickly and steadily, the volume of the precursory gas middle line output part 23 is adjusted so that the precursory gas middle line 22 and the precursory gas middle line output part 23 can be replaced with the purge gas in less than or equal to 2 second with keeping a condition that the period to flow the purge gas is about 5 second.
In addition, comparison was made for four cases of the performance in this embodiment: with the pressure in the chamber 8 of 0.1 Torr, 1 Torr, 10 Torr and 20 Torr.
Generally the pressure in the chamber 8 is, as mentioned above, controlled to be 0.1˜10 Torr. With this pressure, inside of the chamber 8 is replaced by the purge gas. A result concerning attenuation of the concentration of the precursory gas (TMA) is shown in
Under a condition that the concentration of the gas was over 1/1000, namely in case that the pressure in the chamber 8 was 20 Torr, if the gas was switched in 2 second, particles were generated and a number of the particles became more than or equal to about 800 pieces. This is because that the particles (particles of aluminum oxide) are generated due to reaction in a gaseous phase of the chamber 8 since the reactive gas (H2O) is supplied to the chamber 8 under a condition that the replacement of the gas is insufficient.
In this case, generally the period to flow the purge gas is elongated. However, it will elongate the period required for film forming, thereby failing improvement of the throughput.
Consequently, in order to make it possible to purge the inside of the chamber 8 by the use of the purge gas quickly and steadily, it was found that the problem could be solved by purging the inside of the chamber 8 by the use of the purge gas in less than or equal to 2 second with the period to flow the purge gas kept about 5 second, and furthermore by making the concentration of the precursory gas less than or equal to 1/1000.
In order to solve the concrete problem concerning purge of the chamber 8, hardware should be selected appropriately because the volume of the chamber 8 that requires purge gas supply or the capacity of the pump 9 to depressurize the chamber 8 in order to discharge gas quickly from the chamber 8 have an influence on this problem. Then the hardware is appropriately selected so that the period required for purging the chamber 8 by the use of the purge gas is less than or equal to 2 second, the concentration of the precursory gas is less than or equal to 1/1000, and the purge time of the precursory gas middle line output part 23 is less than or equal to 2 second. This arrangement makes it possible to improve the throughput during the process of film forming and to produce the thin film of high quality at a low cost compared with a conventional technique.
In this embodiment, the volume of the chamber 8 is set to be about 2 L (2.2 L), and the pumping speed of the pump 9 is set to be about 280 m3/hr.
The above description is about the precursory gas supplying line 2, however, the same can be said for the reactive gas supplying line 1.
As shown in
As mentioned above, since the metal oxide film that includes particles or whose thickness is uneven is insufficient in film density and mostly defective, quality of the thin film is aggravated.
As a result of this, it was found that the arrangement wherein the reactive gas supplying line 1 and the precursory gas supplying line 2 were independently connected to the chamber 8 was superior.
It was understood that it was not good to use a common line for the precursory gas and the reactive gas, and it was also understood that it was not good to use a common line for different kinds of the precursory gas.
As an example to form a HfAlOx film as a compound oxide film, a schematic diagram of the system by the use of TMA and TDMAH (tetrakis dimethyl amino hafnium: Hf[N(CH3)2]4) as the precursory gas and H2O as the reactive gas is shown in
Since the precursor of TMA and the precursor of TDMAH react each other, there is a concern that particles are generated when the precursory gas supplying line is shared. As a result, it was found that the arrangement of the film forming system wherein each of the gas supplying lines was independently connected to the chamber was better since it could be selected freely without considering a combination of chemical compounds of the precursory gas.
Under the condition of the above-mentioned embodiment, a Al2O3 film (aluminum oxide) was formed with changing an amount of the reactive gas (H2O) to be supplied at a time. The result is shown in
The above-mentioned is a case that the amount of the reactive gas to be supplied is changed, and a case that an amount of the precursory gas to be supplied is changed also will be described. In case of forming a HfO2 film (hafnium oxide) with TDMAH used as the precursory gas and H2O used as the reactive gas, the HfO2 film was formed with changing an amount of the TDMAH gas to be supplied at a time. A result of this is shown in
As mentioned above, the amount of the precursory gas and the reactive gas to be supplied is required to be controlled. As a device to control the amount of the gas to be supplied, there is a method for controlling the concentration of the gas to be supplied by adjusting the pressure of the inside of the middle line 12, 22 by the use of a pump 91, 92 individually in case of filling the gas to each of the middle lines 12, 22.
A concrete arrangement of the film forming system comprising the concentration adjusting device will be described as follows.
As shown in
In order to connect the concentration adjusting device to the chamber 8, the bypath line 4 is removed from the arrangement of the above-mentioned embodiment and the purge gas supplying line 3 is divided into a purge gas supplying line for reactive gas 31 and a purge gas supplying line for precursory gas 31.
In addition, as an alteration of connecting the lines, first the purge gas supplying line for reactive gas 31 and the bypath line for reactive gas 41 are connected through a switching valve 31b, the purge gas supplying line for precursory gas 32 and the bypath line for precursory gas 42 are connected through a switching valve 32b, and next as an alteration of connecting each branch line 31p1, 41p1, 32p2, 42p2, the purge gas supplying branch line for reactive gas 31p1 is connected to the purge gas supplying line for reactive gas 31 and the reactive gas middle line inlet valve 1b1, the bypath branch line for reactive gas 41p1 is connected to the bypath line for reactive gas 41 and the reactive gas middle line outlet valve 1b2, the purge gas supplying branch line for precursory gas 32p2 is connected to the purge gas supplying line for precursory gas 32 and the precursory gas middle line inlet valve 2b1, and the bypath branch line for precursory gas 42p2 is connected to the bypath line for precursory gas 42 and the precursory gas middle line outlet valve 2b2.
In order to adjust the concentration by the use of the film forming system comprising the concentration adjusting device, the reactive gas is continuously sent to the pressure adjusting line for reactive gas 41c and the precursory gas is continuously sent to the pressure adjusting line for precursory gas 42c. Then the concentration of the reactive gas and the concentration of the precursory gas can be made to be a desired constant value at a time of filling the reactive gas and the precursory gas into the reactive gas middle line 12 and the precursory gas middle line 22, and the concentration of the reactive gas and the concentration of the precursory gas at a time when each gas is supplied to the chamber can be made more than or equal to 0.15 μmol/cm2.
In accordance with this invention, a thin film of high quality can be formed in a short time without generating particle, and if this invention is applied especially to semiconductor equipment a very dramatic effect can be obtained such that a gate insulating film, a gate electrode film and a capacitor insulating film of high quality can be formed in a short time with a low cost.
Number | Date | Country | Kind |
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2004-000685 | Jan 2004 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP04/19239 | 12/22/2004 | WO | 00 | 7/10/2007 |