JP2005064538A - Substrate processing device and method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress the formation of an Al film etc., in a nozzle as a by-product at the time of forming an Al<SB>2</SB>O<SB>3</SB>film etc. <P>SOLUTION: A substrate processing device has a reaction pipe 203 and a heater 207 which heats a silicon wafer 200 and forms the Al<SB>2</SB>O<SB>3</SB>film on the surface of the silicon wafer 200 by alternately supplying trimethylaluminum (TMA) and ozone (O<SB>3</SB>) into the reaction pipe 203. The device is also provided with supply pipes 232a and 232b flowing respective the ozone and TMA, and a nozzle 233 which supplies a gas into the reaction pipe 203. The ozone and TMA are respectively supplied into the reaction pipe 203 through the nozzle 233 by connecting the supply pipes 232a and 232b to the nozzle 233 disposed inside of the heater 207 in a temperature region lower than the temperature in the vicinity of the wafer 200 in the reaction pipe 203. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a substrate processing apparatus and a semiconductor device manufacturing method, and more particularly, to a semiconductor manufacturing apparatus for forming a film by an ALD (Atomic layer Deposition) method and a semiconductor device using an ALD method used when manufacturing a Si semiconductor device. It relates to a manufacturing method.

First, a film forming process using an ALD method which is one of CVD (Chemical Vapor Deposition) methods will be briefly described.
In the ALD method, under a certain film formation condition (temperature, time, etc.), two types (or more) of source gases used for film formation are alternately supplied onto the substrate one by one and adsorbed in units of one atomic layer. This is a technique for performing film formation by utilizing surface reaction.
That is, for example, when an Al ₂ O ₃ (aluminum oxide) film is formed, TMA (Al (CH ₃ ) ₃ , trimethylaluminum) and O ₃ (ozone) are alternately supplied using the ALD method. Enables high-quality film formation at a low temperature of 250 to 450 ° C. in this way,
In the ALD method, film formation is performed by alternately supplying a plurality of types of reactive gases one by one. And film thickness control is controlled by the cycle number of reactive gas supply. For example, assuming that the film formation rate is 1 mm / cycle, when a film of 20 mm is formed, the film forming process is performed 20 cycles.

Conventionally, an ALD apparatus for forming an Al ₂ O ₃ film has one substrate processed simultaneously in one processing furnace.
It is of a type called a sheet-to-five sheet device, and has not been put into practical use as a device of a type called a batch type device in which 25 or more substrates are arranged in parallel in the tube axis direction of the reaction tube.

Using TMA and O ₃ to form an Al ₂ O ₃ film with such a vertical batch type apparatus,
When TMA nozzle and O ₃ nozzle are set up in the reactor separately, TMA decomposes in TMA gas nozzle and Al (aluminum) film is formed. was there.

A main object of the present invention is to provide a substrate processing apparatus and a semiconductor device manufacturing method capable of suppressing the generation of foreign matter due to Al film peeling by preventing the formation of an Al film in a nozzle.

According to one aspect of the invention,
A substrate having a processing chamber for storing a substrate and a heating member for heating the substrate, wherein at least two gases that react with each other are alternately supplied into the processing chamber to generate a desired film on the surface of the substrate A processing device comprising:
Two supply pipes through which the two gases flow independently of each other;
A single gas supply member for supplying a gas into the processing chamber, wherein a part of the single gas supply member extends in a region equal to or higher than a decomposition temperature of at least one of the two gases. A supply member,
Connecting the two supply pipes to the gas supply member at a location below the decomposition temperature of the at least one gas, and supplying the two gases into the processing chamber via the gas supply member, respectively. A featured substrate processing apparatus is provided.

  Preferably, the gas supply member is a nozzle having a large number of gas ejection ports.

Preferably, the connection point between the two supply pipes and the gas supply member is in the processing chamber.

According to another aspect of the invention,
A processing chamber that accommodates the substrate; and a heating member that is disposed outside the processing chamber and that heats the substrate. At least two gases that react with each other are alternately supplied into the processing chamber, and A substrate processing apparatus including a hot wall type processing furnace for generating a desired film on a surface,
Two supply pipes through which the two gases flow independently of each other;
A single gas supply member for supplying gas into the processing chamber, and a part of the single gas supply member disposed inside the heating member,
The two supply pipes are connected to the gas supply member in a region having a temperature lower than the temperature in the vicinity of the substrate in the processing chamber, and the two gases are respectively supplied to the processing chamber through the gas supply member. A substrate processing apparatus is provided.

According to yet another aspect of the invention,
A substrate having a processing chamber for storing a substrate and a heating member for heating the substrate, wherein at least two gases that react with each other are alternately supplied into the processing chamber to generate a desired film on the surface of the substrate A processing device comprising:
Two supply pipes through which the two gases flow independently of each other;
A single gas supply member for supplying a gas into the processing chamber, wherein a part of the single gas supply member extends in a region equal to or higher than a decomposition temperature of at least one of the two gases. A supply member,
Substrate processing that connects the two supply pipes to the gas supply member at a location below the decomposition temperature of the at least one gas and supplies the two gases into the processing chamber via the gas supply member, respectively. Using the device,
A method of manufacturing a semiconductor device is provided, wherein the two gases are alternately supplied into the processing chamber via the gas supply member to generate the desired film on the surface of the substrate.

It is possible to form an Al ₂ O ₃ film or the like by the ALD method with a batch type processing apparatus excellent in mass productivity, and to suppress the formation of an Al film or the like in a nozzle that is a by-product.

In a batch processing apparatus of a preferred embodiment of the present invention, a substrate capable of holding a plurality of substrates by using trimethylaluminum (chemical formula Al (CH ₃ ) ₃ , TMA) and ozone (O ₃ ) as raw materials. A holding jig, a reaction tube in which the substrate holding jig is inserted to process the substrate, a heating means for heating the substrate, a vacuum exhaust device capable of exhausting the gas in the reaction tube, and a substrate surface direction with respect to the substrate A gas nozzle that jets gas in parallel with the gas, and TMA and O ₃ gas supply lines connected to the nozzle merge in the reaction chamber to supply TMA and O ₃ alternately onto the substrate. Then, an aluminum oxide film (Al ₂ O ₃ film) is formed. In addition, TM on the substrate
A is adsorbed, and the O ₃ gas to be flowed next reacts with the adsorbed TMA to produce a monolayer Al ₂ O ₃ film.

In TMA, when both pressure and temperature are increased, self-decomposition is likely to occur, and an Al film is generated. The gas nozzle is provided with a nozzle hole for ejecting gas. Since the nozzle hole is small, the pressure in the nozzle is higher than the pressure in the furnace. For example, the furnace pressure is 0.5 To
At rr (about 67 Pa), the pressure inside the nozzle is expected to be 10 Torr (about 1330 Pa). For this reason, TMA self-decomposition tends to occur particularly in a nozzle in a high temperature region. In contrast, the temperature is high in the furnace, but the pressure is not as high as in the nozzle.
TMA self-degradation is difficult to occur. Therefore, the problem of Al film generation in the nozzle becomes significant.

In order to remove the Al ₂ O ₃ film adhering to the inner wall of the reaction tube, cleaning is performed by flowing a ClF ₃ gas. If this cleaning gas is supplied from the nozzle, the Al ₂ O in the nozzle is removed.
_{The three} films can be removed at the same time, and cleaning can be made easier and more efficient.

Further, the present invention is suitably applied not only to the generation of an Al ₂ O ₃ film but also to the generation of an HfO ₂ film. This is because the Hf raw material has the same problem as TMA. In this case, the HfO ₂ film is formed by alternately flowing Hf source gas of vaporized tetrakis (N-ethyl-N-methylamino) hafnium (liquid at room temperature) and O ₃ gas.
Furthermore, the present invention is also suitably applied to the generation of a SiO ₂ film using the following materials.
(1) O ₃ and Si ₂ cl ₆ (hexachlorodisilane) are allowed to flow alternately to form S by ALD.
When forming an iO ₂ film.
(2) O ₃ and HSi (OC ₂ H ₅ ) ₃ (TRIES) are allowed to flow alternately and ALD is used for S
When forming an iO ₂ film.
(3) _{O 3} and _{HSi [N (CH 3) 2} ] 3 (TrisDMAS) and flowing alternately ALD
When the SiO ₂ film is formed by the method.

FIG. 1 is a schematic configuration diagram of a vertical substrate processing furnace according to the present embodiment, showing a processing furnace portion in a vertical cross section, and FIG. 2 is a schematic configuration diagram of a vertical substrate processing furnace according to the present embodiment. Yes, the processing furnace part is shown in cross section. FIG. 3 is a view for explaining the nozzle 233 of the vertical substrate processing furnace in the substrate processing apparatus of the present embodiment, FIG. 3A is a schematic view, and FIG. 3B is a partially enlarged view of part A of FIG. 3A. is there.

A reaction tube 203 is provided inside the heater 207 as a heating means as a reaction vessel for processing the wafer 200 as a substrate, and a manifold 209 made of, for example, stainless steel is engaged with the lower end of the reaction tube 203. The lower end opening is a seal cap 21 which is a lid.
9, the process furnace 202 is formed by at least the heater 207, the reaction tube 203, the manifold 209, and the seal cap 219. The manifold 209 has a holding means (hereinafter referred to as a heater base 251).
Fixed to.

An annular flange is provided at each of the lower end portion of the reaction tube 203 and the upper opening end portion of the manifold 209, and an airtight member (hereinafter referred to as an O-ring 220) is disposed between these flanges. Has been.

The seal cap 219 has a boat 21 as a substrate holding means through a quartz cap 218.
7 is erected, and the quartz cap 218 is a holding body for holding the boat 217. Then, the boat 217 is inserted into the processing furnace 202. A plurality of wafers 200 to be batch-processed are stacked on the boat 217 in a horizontal posture in multiple stages in the tube axis direction. The heater 207 is a processing furnace 202.
The wafer 200 inserted in is heated to a predetermined temperature.

The processing furnace 202 is provided with two gas supply pipes 232a and 232b as supply pipes for supplying a plurality of types, here two types of gases. The gas supply pipes 232a and 232b are provided through the lower portion of the manifold 209, and the gas supply pipe 232b is provided in the processing furnace 202.
The two gas supply pipes 232 a and 232 b communicate with one porous nozzle 233 by joining with the gas supply pipe 232 a. The nozzle 233 is provided in the processing furnace 202, and its upper portion extends in a region that is equal to or higher than the decomposition temperature of TMA supplied from the gas supply pipe 232b.
However, the location where the gas supply pipe 232b merges with the gas supply pipe 232a in the processing furnace 202 is an area below the decomposition temperature of TMA, and is in an area where the temperature is lower than the temperature of the wafer 200 and the vicinity of the wafer 200. is there. Here, from the first gas supply pipe 232a, a first mass flow controller 241a which is a flow rate control means and a first valve 243a which is an on-off valve.
Through the perforated nozzle 233 installed in the processing furnace 202 to be described later.
The reaction gas (O ₃ ) is supplied to 02, and a second mass flow controller 241b as a flow rate control unit, a second valve 252 as an on-off valve, and TMA are supplied from the second gas supply pipe 232b.
The porous nozzle 233 described above is passed through the container 260 and the third valve 250 which is an on-off valve.
The reaction gas (TMA) is supplied to the processing furnace 202 through the above. The gas supply pipe 232b from the TMA container 260 to the manifold 209 is provided with a heater 300, and the gas supply pipe 23
2b is kept at 50-60 ° C.

An inert gas line 232 c is connected to the gas supply pipe 232 b on the downstream side of the third valve 250 via the open / close valve 253. In addition, an inert gas line 232d is connected to the gas supply pipe 232a on the downstream side of the first valve 243a via an open / close valve 254.

The processing furnace 202 has a fourth valve 24 by a gas exhaust pipe 231 which is an exhaust pipe for exhausting gas.
It is connected to a vacuum pump 246 which is an evacuation means through 3d, and is evacuated. The fourth valve 243d is an open / close valve that can open and close the valve to stop evacuation / evacuation of the processing furnace 202, and further adjust the valve opening to adjust the pressure.

A nozzle 233 is disposed along the stacking direction of the wafer 200 from the lower part to the upper part of the reaction tube 203. The nozzle 233 is provided with gas supply holes 248b which are supply holes for supplying a plurality of gases.

A boat 217 for mounting a plurality of wafers 200 in multiple stages at the same interval is provided at the center of the reaction tube 203. The boat 217 can enter and exit the reaction tube 203 by a boat elevator mechanism (not shown). It has become. In order to improve processing uniformity, boat 2
A boat rotating mechanism 267 that is a rotating means for rotating the boat 17 is provided, and the boat 217 held by the quartz cap 218 is rotated by rotating the boat rotating mechanism 267.

The controller 121, which is a control means, includes first and second mass flow controllers 241a.
, 241b, first to fourth valves 243a, 252, 250, 243d, valve 253,
254, a heater 207, a vacuum pump 246, a boat rotation mechanism 267, and a boat elevating mechanism not shown in the drawing, and the flow rate adjustment of the first and second mass flow controllers 241a and 241b, the first to third valves 243a. 252 and 250, opening and closing operation of the valves 253 and 254, opening and closing of the fourth valve 243d and pressure adjusting operation, temperature adjustment of the heater 207, starting and stopping of the vacuum pump 246, adjustment of the rotation speed of the boat rotating mechanism 267, and raising and lowering of the boat The mechanism is controlled to move up and down.

Next, as an example of film formation by the ALD method, a case where an Al ₂ O ₃ film is formed using TMA and O ₃ gas will be described.
First, a semiconductor silicon wafer 200 to be deposited is loaded into a boat 217, and the processing furnace 2
Carry in 02. After carrying in, the following three steps are sequentially executed.

[Step 1]
In step 1, O ₃ gas is flowed. First, the first valve 243a provided in the first gas supply pipe 232a and the fourth valve 243d provided in the gas exhaust pipe 231 are both opened, and the first mass flow controller 243a is operated from the first gas supply pipe 232a. O with adjusted flow rate
₃ gas exhaust pipe 2 while supplying gas from gas supply hole 248b of nozzle 233 to processing furnace 202
31 is exhausted. When the O ₃ gas is allowed to flow, the pressure in the processing furnace 202 is set to 10 to 100 Pa by appropriately adjusting the fourth valve 243d. The supply flow rate of O ₃ controlled by the first mass flow controller 241a is 1000 to 10,000 sccm. The time for exposing the wafer 200 to O ₃ is 2 to 120 seconds. At this time, the temperature of the heater 207 is a wafer temperature of 250 to
It is set to 450 ° C.

At the same time, when the opening / closing valve 253 is opened from the inert gas line 232c connected to the middle of the gas supply pipe 232b to flow the inert gas, it is possible to prevent the O ₃ gas from flowing into the TMA side.

At this time, the gases flowing into the processing furnace 202 are only inert gases such as O ₃ , N ₂ , and Ar, and there is no TMA. Therefore, O ₃ does not cause a gas phase reaction, and reacts with the underlying film on the wafer 200.

[Step 2]
In step 2, the first valve 243a of the first gas supply pipe 232a is closed to stop the supply of O ₃ . Further, the fourth valve 243 d of the gas exhaust pipe 231 is kept open, and the processing furnace 202 is exhausted to 20 Pa or less by the vacuum pump 246, and residual O ₃ is removed from the processing furnace 202. At this time, if an inert gas such as N ₂ is supplied to the processing furnace 202 from the first gas supply pipe 232a that is an O ₃ supply line and the second gas supply pipe 232b that is a TMA supply line, respectively, The effect of eliminating O ₃ is further enhanced.

[Step 3]
In step 3, TMA gas is flowed. TMA is a liquid at room temperature, and in order to supply it to the processing furnace 202, a method of supplying it after heating and vaporizing, passing an inert gas such as nitrogen or a rare gas called a carrier gas through the TMA container 260, There is a method of supplying the vaporized part to the processing furnace together with the carrier gas, and the latter case will be described as an example. First, the valve 252 provided in the carrier gas supply pipe 232b, the valve 250 provided between the TMA container 260 and the processing furnace 202, and the fourth valve 243d provided in the gas exhaust pipe 231 are opened, and the carrier gas supply pipe is opened. The carrier gas whose flow rate has been adjusted by the second mass flow controller 241b from 232b passes through the TMA container 260, and is supplied to the processing furnace 202 through the gas supply hole 248b of the nozzle 233 as a mixed gas of TMA and carrier gas. Exhaust from the tube 231. When flowing TMA gas, the fourth valve 243d is appropriately adjusted so that the pressure in the processing furnace 202 is 10 to 900 Pa. Second mass flow controller 241
The supply flow rate of the carrier gas controlled by a is 10,000 sccm or less. The time for supplying TMA is set to 1 to 4 seconds. Thereafter, the time for exposure to an elevated pressure atmosphere for further adsorption may be set to 0 to 4 seconds. At this time, the wafer temperature is the same as when O ₃ is supplied.
250-450 ° C. By supplying TMA, O ₃ on the base film and TMA react with each other to form an Al ₂ O ₃ film on the wafer 200.

At the same time, when the opening / closing valve 254 is opened from the inert gas line 232d connected in the middle of the gas supply pipe 232a to flow the inert gas, it is possible to prevent the TMA gas from flowing into the O ₃ side.

After the film formation, the valve 250 is closed, the fourth valve 243d is opened, and the processing furnace 202 is evacuated to remove the gas after contributing to the film formation of the remaining TMA. Further, at this time, if an inert gas such as N ₂ is supplied to the processing furnace 202 from the first gas supply pipe 232a which is an O ₃ supply line and the second gas supply pipe 232b which is a TMA supply line, the residual gas is further increased. The effect of removing the gas after contributing to the film formation of TMA from the processing furnace 202 is enhanced.

Steps 1 to 3 are defined as one cycle, and this cycle is repeated a plurality of times to form an Al ₂ O ₃ film having a predetermined thickness on the wafer 200.

Since the inside of the processing furnace 202 is evacuated to remove the O ₃ gas, TMA is flown, so that they do not react on the way to the wafer 200. The supplied TMA can effectively react only with O ₃ adsorbed on the wafer 200.

Further, the TMA and the O ₃ are alternately arranged in the nozzle 233 by joining the first gas supply pipe 232a which is an O ₃ supply line and the second gas supply pipe 232b which is a TMA supply line in the processing furnace 202. The deposited film can be made Al ₂ O ₃ by adsorption and reaction, and TMA
It is possible to eliminate the problem of the Al film that can be a foreign substance source within TMA nozzle when supplying O ₃ at different nozzles to produce a. Since the Al ₂ O ₃ film has better adhesion than the Al film and is less likely to peel off, it is less likely to become a foreign matter generation source.

Next, with reference to FIG. 4, the outline about the semiconductor manufacturing apparatus which is an example of the substrate processing apparatus to which this invention is applied suitably is demonstrated.

A cassette stage 105 is provided on the front side of the inside of the housing 101 as a holder transfer member that transfers the cassette 100 as a substrate storage container to and from an external transfer device (not shown). Is provided with a cassette elevator 115 as an elevating means, and a cassette transfer machine 114 as a conveying means is attached to the cassette elevator 115. Further, a cassette shelf 109 as a means for placing the cassette 100 is provided on the rear side of the cassette elevator 115, and a spare cassette shelf 110 is also provided above the cassette stage 105. A clean unit 11 is located above the spare cassette shelf 110.
8 is provided so that clean air is circulated through the inside of the housing 101.

A processing furnace 202 is provided above the rear portion of the housing 101, and a boat 217 as a substrate holding unit that holds the wafers 200 as substrates in a horizontal posture in multiple stages is raised and lowered to the processing furnace 202 below the processing furnace 202. A boat elevator 121 as an elevating means is provided, and a seal cap 219 as a lid is attached to the tip of an elevating member 122 attached to the boat elevator 121 to support the boat 217 vertically. Between the boat elevator 121 and the cassette shelf 109, a transfer elevator 113 as an elevating means is provided, and a wafer transfer machine 112 as a transfer means is attached to the transfer elevator 113. Further, a furnace port shutter 116 as a shielding member having an opening / closing mechanism and closing the lower surface of the processing furnace 202 is provided beside the boat elevator 121.

The cassette 100 loaded with the wafers 200 is loaded from the external transfer device (not shown) onto the cassette stage 105 in an upward posture, and is rotated by 90 ° C. on the cassette stage 105 so that the wafer 200 is in a horizontal posture. Further, the cassette 100 is transported from the cassette stage 105 to the cassette shelf 109 or the spare cassette shelf 110 by cooperation of the raising / lowering operation of the cassette elevator 115, the transverse operation, the advance / retreat operation of the cassette transfer machine 114, and the rotation operation.

The cassette shelf 109 has a transfer shelf 123 in which the cassette 100 to be transferred by the wafer transfer device 112 is stored. The cassette 100 to which the wafer 200 is transferred is transferred by the cassette elevator 115 and the cassette transfer device 114. Transferred to the transfer shelf 123.

When the cassette 100 is transferred to the transfer shelf 123, the wafers 200 are transferred from the transfer shelf 123 to the boat 217 in a lowered state by the cooperation of the advance / retreat operation, the rotation operation, and the lifting / lowering operation of the transfer elevator 113. Is transferred.

When a predetermined number of wafers 200 are transferred to the boat 217, the boat 217 is inserted into the processing furnace 202 by the boat elevator 121, and the processing furnace 202 is hermetically closed by the seal cap 219. In the processing furnace 202 that is hermetically closed, the wafer 200 is heated and a processing gas is supplied into the processing furnace 202 to process the wafer 200.

When the processing on the wafer 200 is completed, the wafer 200 is subjected to the reverse procedure of the operation described above.
It is transferred from the boat 217 to the cassette 100 of the transfer shelf 123, the cassette 100 is transferred from the transfer shelf 123 to the cassette stage 105 by the cassette transfer device 114, and is carried out of the housing 101 by an external transfer device (not shown). Is done. In addition, the furnace port shutter 116 is connected to the boat 2.
When 17 is in the lowered state, the lower surface of the processing furnace 202 is closed to prevent outside air from being caught in the processing furnace 202.
The transport operation of the cassette transfer machine 114 and the like is controlled by the transport control means 124.

It is a schematic longitudinal cross-sectional view of the vertical substrate processing furnace in the substrate processing apparatus of one Example of this invention. 1 is a schematic cross-sectional view of a vertical substrate processing furnace in a substrate processing apparatus according to an embodiment of the present invention. 3A and 3B are diagrams for explaining a nozzle 233 of a vertical substrate processing furnace in a substrate processing apparatus according to an embodiment of the present invention, FIG. 3A is a schematic view, and FIG. 3B is a partially enlarged view of part A in FIG. 3A. . It is a schematic oblique view for demonstrating the substrate processing apparatus of one embodiment of this invention.

Explanation of symbols

121 ... Controller 200 ... Wafer 202 ... Processing furnace 203 ... Reaction tube 207 ... Heater 209 ... Manifold 217 ... Boat 218 ... Quartz cap 219 ... Seal cap 220 ... O-ring 231 ... Gas exhaust pipe 232a ... First gas supply pipe 232b ... Second gas supply pipe 232c ... inert gas line 232d ... inert gas line 233 ... nozzle 241a ... first mass flow controller 241b ... second mass flow controller 243a ... first valve 243d ... fourth valve 246 ... vacuum Pump 248b ... Gas supply hole 250 ... Third valve 251 ... Heater base 252 ... Second valve 253 ... Valve 254 ... Valve 260 ... TMA container 267 ... Boat rotation mechanism 300 ... Heater

Claims (1)

A substrate having a processing chamber for storing a substrate and a heating member for heating the substrate, wherein at least two gases that react with each other are alternately supplied into the processing chamber to generate a desired film on the surface of the substrate A processing device comprising:
Two supply pipes through which the two gases flow independently of each other;
A single gas supply member for supplying a gas into the processing chamber, wherein a part of the single gas supply member extends in a region equal to or higher than a decomposition temperature of at least one of the two gases. A supply member,
Connecting the two supply pipes to the gas supply member at a location below the decomposition temperature of the at least one gas, and supplying the two gases into the processing chamber via the gas supply member, respectively. A substrate processing apparatus.

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