JP2010103495A - Semiconductor device, and apparatus and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor device having the degree of freedom in forming oxide films so that an oxide film containing reduced or no nitride component is formed at a low temperature and a thick oxide film is formed at a low temperature by a batch system growth device. <P>SOLUTION: A silicon-based gas containing alkyl group or alkoxy group or a siloxane gas or a silazane gas is allowed to react to an oxidizer for oxidizing the gas at ≤500°C in a depressurized state. A silane gas, a disilane gas, a phosphorus gas or a boron gas is allowed to react as an additive to the gas. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a semiconductor device, a manufacturing apparatus and a manufacturing method thereof, and more particularly to a semiconductor device, a manufacturing apparatus and a manufacturing method thereof, which form a silicon oxide film (hereinafter sometimes referred to as an oxide film) at a low temperature.

  Conventionally, there has been a technique for forming an SiON film as an oxide film on a glass substrate by reacting ozone gas and hexamethyldisilazane gas at a low temperature of about 200 ° C.

  However, when ozone gas and hexamethyldisilazane gas are reacted, the oxide film that can be formed on the glass substrate is only a SiON film as described above. That is, the conventional method has no flexibility in forming the oxide film. In addition, an oxide film that does not reduce or contain nitrogen components at low temperatures has not been formed. Furthermore, there is no method for forming a thick oxide film at a low temperature in a batch growth apparatus.

  Accordingly, it is an object of the present invention to provide flexibility in forming an oxide film, to form an oxide film that does not contain or reduce nitrogen components at a low temperature, and to form a thick oxide film.

In order to solve the above problems, a semiconductor device manufacturing apparatus according to the present invention includes:
A means for supplying a silane-based gas or a siloxane-based gas or a silazane-based gas containing at least one selected from an alkyl group, an alkoxy group, and an amino group; a means for supplying an oxidant; and the gas and the oxidant in a reduced pressure state. A means for reacting at a temperature of 500 ° C. or lower is provided.

  Furthermore, it is possible to provide means for reacting at a temperature of 400 ° C. or lower in a plasma state. In addition, when it is desired to form a thick oxide film or an oxide film at a lower temperature, a means for reacting the gas with a silane gas, disilane gas, phosphorus-based gas, or boron-based gas as an additive is provided. It is valid. The temperature may be lowered to a temperature below the boiling point of the gas. Furthermore, when it is desired to form a dense oxide film, it is effective to provide means for performing an annealing process using ozone gas or ultraviolet irradiation after the reaction. Furthermore, in order to control the oxidation reaction, a means for diluting the oxidizing agent with an inert gas may be provided.

In addition, a method for manufacturing a semiconductor device of the present invention includes:
Introducing a silicon-based gas or siloxane gas or silazane gas containing an alkyl group or an alkoxy group onto a substrate heated below the boiling point of these gases (A);
A step (B) of introducing an oxidant and reacting with the gas under a reduced pressure at a temperature of 500 ° C. or lower;

  Furthermore, the semiconductor device of the present invention of the present invention has a design rule of 32 nm or less, and the source region and the drain region are not in physical contact.

  The silane-based gas, siloxane-based gas, or silazane-based gas (hereinafter sometimes referred to as silicon-based gas) containing at least one selected from an alkyl group, an alkoxy group, and an amino group according to the present invention is formed. The molecular structure, which is a precursor for supplying silicon atoms to the oxide film, has an alkyl group or an alkoxy group, and the alkyl group and alkoxy group are preferably bonded directly to the silicon atom. Further, a compound composed of a compound having at least one H group is preferably used since it has excellent step coverage.

Examples of the silane-based gas containing at least one selected from an alkyl group, an alkoxy group, and an amino group include trimethoxysilane (HSi (OCH ₃ ) ₃ ) gas, triethoxysilane (HSi (OC ₂ H ₅ ) ₃ ) gas, methyldimethoxysilane _{(HSi (CH 3) (OCH} 3) 2) gas, methyl diethoxy silane _{(HSi (CH 3) (OC} 2 H 5) 2) gas, dimethyl methoxy silane _{(HSi (CH 3) 2 (} OCH 3 )) gas, dimethylethoxysilane _{(HSi (CH 3) 2 (} OC 2 H 5)) gas, tetramethoxysilane (Si _{(OCH 3) 4)} gas, tetraethoxysilane _{(Si (OC 2 H 5)} 4) gas , aminosilane gas, diaminosilanes _{(H 2 Si (NH 2)} 2) gas, triamino silanes (HSi (NH ) ₃₎ gas, tetra aminosilane (Si _{(NH 2) 4)} gas, dimethylamino silane _(H 3 SiN _{(CH 3) 2)} gas, bis (dimethylamino) silane _{(H 2 Si (N (CH} 3) 2) 2 ) Gas, tris (dimethylamino) silane (HSi (N (CH ₃ ) ₂ ) ₃ ) gas, and tetrakis (dimethylamino) silane (Si (N (CH ₃ ) ₂ ) ₄ ) gas.

Examples of the siloxane-based gas include disiloxane ((H ₃ Si) ₂ O) gas, dimethyldisiloxane ([H ₂ (CH ₃ ) Si] ₂ O) gas, and tetramethyldisiloxane ([H (CH ₃ ) ₂ Si). ] ₂ O) gas, dimethyldimethoxydisiloxane ([H (CH ₃ ) (CH ₃ O) Si] ₂ O) gas, tetramethoxydisiloxane ([H (CH ₃ O) ₂ Si] ₂ O) gas, tetra Methyldimethoxydisiloxane ([(CH ₃ ) ₂ (CH ₃ O) Si] ₂ O) gas, dimethyldiethoxydisiloxane ([H (CH ₃ ) (C ₂ H ₅ O) Si] ₂ O) gas, tetra ethoxy disiloxane include _{([H (C 2 H 5} O) 2 Si] 2 O) gas.

Examples of the silazane-based gas include disilazane ((H ₃ Si) ₂ NH) gas, dimethyl disilazane ([H ₂ (CH ₃ ) Si] ₂ NH) gas, and tetramethyldisilazane ([H (CH ₃ ) ₂ Si]. ₂ NH) gas, dimethyldimethoxydisilazane ([H (CH ₃ ) (CH ₃ O) Si] ₂ NH) gas, dimethyldiethoxydisilazane ([H (CH ₃ ) (C ₂ H ₅ O) Si] ₂ NH) include gas, tetraethoxy disilazane _{([H (C 2 H 5} O) 2 Si] 2 NH) gas, dimethoxy tetramethyl disilazane _{([(OCH 3) (CH} 3) 2 Si] is 2 NH) gas It is done.

The oxidant according to the present invention is a substance that reacts with the silicon-based gas to form an oxide film. Examples of the oxidizing agent include oxygen (O ₂₎ , water (H ₂ O), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), and the like. These may be used alone or in combination of two or more. can do. Further, the oxidizing agent may be diluted with a reaction inert gas such as nitrogen gas, helium gas, neon gas, or argon gas. As the oxidizer, oxygen (O ₂ ), water (H ₂ O), and ozone (O ₃ ) are preferable because the obtained oxide film has good film quality and is easy to handle.

  The additive according to the present invention is used for controlling the film quality of the formed oxide film or for promoting or suppressing the oxide film forming reaction. The additive includes silane gas, disilane gas, and phosphorus-based gas. Or a boron-type gas is mentioned. Examples of phosphorus-based gases include phosphine gas, trimethyl phosphite gas, trimethyl phosphate gas, triethyl phosphite gas, triethyl phosphate gas, and boron-based gases include borane gas, diborane gas, trimethyl borate gas, and triethyl borate. Gas etc. are mentioned.

It is a typical block diagram of the semiconductor manufacturing apparatus of Embodiment 1 of this invention. It is a typical block diagram of the 1st chamber 1 of FIG. It is a typical block diagram of the 2nd chamber 2 of FIG. It is typical sectional drawing of the wafer 41 shown in FIG. It is a typical block diagram of the 1st chamber 5 which concerns on Embodiment 2 of this invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be described below with reference to the drawings.
(Embodiment 1)
FIG. 1 is a schematic configuration diagram of a semiconductor manufacturing apparatus according to Embodiment 1 of the present invention. In FIG. 1, a hoop 1 in which a wafer is accommodated, a wafer alignment 2 for positioning a wafer taken out from the hoop 1, a load lock chamber 3 having a load lock mechanism, and an oxide film are formed on the wafer. A first chamber 5 serving as a processing chamber for processing, a second chamber 6 serving as a processing chamber for irradiating an oxide film formed in the first chamber 5 with ultraviolet light, a load lock chamber 3 and a first chamber. 5 shows a transfer chamber 4 having a robot arm for transferring a wafer between 5 and a second chamber 6.

FIG. 2 is a schematic configuration diagram of the first chamber 5 of FIG. FIG. 2 shows a gas supply pipe 71 of trimethylsilane (HSi (CH ₃ ) ₃ ) gas that is a silicon-based gas, and gas supply of water vapor, oxygen (O ₂ ) gas, and ozone (O ₃ ) gas that are oxidants. A pipe 72, a gas supply pipe 73 of helium (He) gas, which is an inert gas, and a gas supply pipe 74 of nitrogen (N ₂ ) gas are shown.

  Each gas supply pipe 71 and the like are connected to the collective pipe 13 via the valve 16 and the mass flow controller 15, respectively. A valve 14 for switching the introduction path of various gases passing through the collecting pipe 13 to the first chamber 5 is attached to the collecting pipe 13. A gas shower for spraying the gas passing through the collecting pipe 13 onto the wafer (glass substrate) 41 is provided downstream of the valve 14. This gas shower includes a gas dispersion plate 31 for introducing the gas into the first chamber 5 at a uniform concentration, and a shower plate 32 provided downstream of the gas dispersion plate 31 and having a plurality of openings 33 formed therein. have.

FIG. 2 also shows a nitrogen trifluoride (NF ₃ ) gas supply pipe 81, an O ₂ gas supply pipe 82, and an argon (Ar) gas supply pipe 83.

  Each gas supply pipe 81 and the like are also connected to the collective pipe 12 through the valve 16 and the mass flow controller 15, respectively. A remote plasma device 21 is attached to the collective pipe 12 to convert various gases passing through the gas supply pipes 81 and the like into plasma before being introduced into the first chamber 5. An RF oscillator 11 for generating plasma is attached in the vicinity of the remote plasma device 21.

  The first chamber 5 includes a heater 51 made of an insulator (AlN or Al) for heating the wafer 41, lift pins 52 for receiving the wafer 41 conveyed by the transfer chamber 4, and a lift pin 52 for raising and lowering the lift pins 52. A drive mechanism 53, an exhaust valve 62 for exhausting the gas in the first chamber 5, and an exhaust pump 61 connected to the exhaust valve 62 are connected.

FIG. 3 is a schematic configuration diagram of the second chamber 6 of FIG. FIG. 3 shows a plurality of (for example, four) lamps 101 such as low-pressure mercury lamps, Xe excimer lamps, and metal halide lamps that irradiate ultraviolet light. A quartz pipe 102 for preventing contact of oxygen, silicon-based gas, or carbon-containing material by-produced in the oxide film formation reaction, N ₂ gas or inert gas 103 supplied into the quartz pipe 102, and continuously and periodically. A light receiving sensor 104 which is intermittently measured in the quartz pipe 102 for measuring the illuminance of the irradiation light from the lamp 101 or externally, or for supplying N ₂ gas into the second chamber 6. a gas supply pipe 75, for supplying an O ₂ gas for cleaning the inside of the second chamber 6 after processing the wafer 41 A gas supply pipe 77 illustrates a gas supply pipe 78 for supplying the O ₃ gas is an alternative gas O ₂ gas of the gas pipe 77. If necessary, it may be able to supply the inert gas in place of N ₂ gas into the second chamber 6. Moreover, you may prepare one chamber which used the 1st chamber 5 and the 2nd chamber 6 together. Specifically, this can be realized by providing a lamp 101 or the like in the first chamber 5.

  Next, a processing procedure of the wafer 41 by the semiconductor manufacturing apparatus shown in FIG. 1 will be described. In the present embodiment, first, a wafer 41 that is, for example, a glass substrate is transferred from a cleaning device in a clean room (not shown) while being accommodated in the FOUP 1. Thereafter, the wafer 41 is taken out from the hoop 1 and transferred to the wafer alignment 2 side.

  In the wafer alignment 2, the wafer 41 is positioned. Thereafter, the wafer 41 is transferred to the load lock chamber 3 prior to being transferred to the first chamber 5.

  Next, the pressure inside the load lock chamber 3 is reduced. When the pressure inside the load lock chamber 3 reaches a desired pressure, the gate valve that partitions the load lock chamber 3 and the transfer chamber 4 is opened.

  Thereafter, the wafer 41 is transferred into the transfer chamber 4. Subsequently, the wafer 41 is transferred from the load lock chamber 3 to the first chamber 5 by the robot arm in the transfer chamber 4.

  In the first chamber 5, the heater 51 is set so that the surface temperature of the wafer 41 is in a range of 50 ° C. to 300 ° C. (for example, 200 ° C.). Next, the wafer (glass substrate) 41 is placed on the lift pins 52 that are positioned above the fixed heater 51 in advance, and then the lift pins 52 are lowered by the drive mechanism 53 so that the wafer 41 is heated. 51.

  Alternatively, the movable heater 51 may be lowered in advance and the wafer 41 may be placed on the lift pins 52 and then the heater 51 may be raised to place the wafer 41 on the heater 51. In the first chamber, the exhaust pump 61 is already turned on, and the exhaust valve 62 is opened to exhaust the interior of the first chamber 5. At this time, the pressure in the first chamber 5 may be about 67 Pa to 201 Pa (for example, 133 Pa).

  Next, each valve 16 is opened under the control of each mass flow controller 15 related to the gas supply pipes 71 and 72, and trimethylsilane gas is directed to the first chamber 5 at 50 cc / min to 100 cc / min (for example, 75 cc / min), water vapor. Is supplied at a flow rate of 200 cc / min to 1000 cc / min (for example, 600 cc / min), and He gas is supplied at a flow rate of 50 cc / min to 150 cc / min (for example, 100 cc / min). In this state, the inside of the chamber is set to 67 Pa to 399 Pa (133 Pa), a high frequency of 13.56 MHz is oscillated from the RF transmitter 11, turned on for several tens of seconds to several minutes (for example, one minute), and 500 W to 650 W The above gases are converted into plasma at an output of (for example, 630 W).

  As a result, an oxide film having a thickness of about 100 nm is formed on the wafer 41. Thereafter, each valve 16 is closed, and introduction of trimethylsilane gas or the like into the first chamber 5 is stopped. In other words, the introduction time of trimethylsilane gas or the like is, for example, 1 minute.

  Then, the wafer 41 is transferred from the first chamber 5 to the second chamber 6 by the robot arm in the transfer chamber 4.

In the second chamber 6, the heater 51 is set so that the surface temperature of the wafer 41 is in a range of 200 ° C. to 400 ° C. (for example, 300 ° C.). Next, the wafer 41 is placed on the heater 51. In the second chamber 6, the exhaust pump 61 is already turned on, N ₂ gas is allowed to flow from 100 cc / min to 300 cc / min (for example, 200 cc / min), the exhaust valve 62 is opened, and the pressure in the second chamber 6 is increased. Exhaust is performed under conditions of 67 Pa to 399 Pa (for example, 133 Pa).

Then, the low-pressure mercury lamp 101 is irradiated with low-pressure mercury light having a power of 10 mW / cm ² within a range in which the throughput does not decrease, so that the ultraviolet annealing process of the wafer 41 is performed. .

An N-type amorphous silicon film was formed on a glass substrate wafer 41 with a thickness of about 100 nm, and an SiO ₂ film was formed thereon with a thickness of about 100 nm. The SiO ₂ film was subjected to ultraviolet annealing. Then, further N-type Hameau fastest silicon film to 100nm formed thereon, patterning, after applying voltage 200V and the temperature 300 ° C. and for 4 hours and below the Hameau Fas silicon film, _{V FB} shift by C-V measurement As a result, the fact that sodium or the like was diffusing from the wafer 41 of the glass substrate was not recognized.

  Further, the thickness of the oxide film formed on the wafer 41 was reduced by about 5% by the ultraviolet annealing process. The refractive index of this oxide film was about 1.55 on average.

On the other hand, the first chamber 5 is cleaned for every 10 wafers 41 processed. Specifically, the valve 16 is opened under the control of the mass flow controller 15, and the NF ₃ gas having a flow rate of about 400 cc / min and the flow rate of about 200 cc / min are introduced into the first chamber 5 through the gas supply pipes 81 to 83. A mixed gas of O ₂ gas and Ar gas at a flow rate of about 100 cc / min is output to the remote plasma apparatus 21.

  Then, the remote plasma device 21 is turned on to turn each gas into plasma and introduce it into the remote plasma device 21. At this time, the interior of the first chamber 5 is exhausted by turning on the exhaust pump 61 and opening the exhaust valve 62. The pressure in the first chamber 5 at the time of exhausting may be about 67 Pa to 133 Pa.

In this embodiment, an example in which an oxide film is formed using trimethylsilane gas has been described. Instead, trimethoxysilane (HSi (OCH ₃ ) ₃ ) gas, triethoxysilane (HSi (OC ₂ H) _{5) 3)} gas, methyldimethoxysilane _{(HSi (CH 3) (OCH} 3) 2) gas, methyl diethoxy silane _{(HSi (CH 3) (OC} 2 H 5) 2) gas, dimethyl methoxy silane (HSi (CH ₃ ) ₂ (OCH ₃ )) gas, dimethylethoxysilane (HSi (CH ₃ ) ₂ (OC ₂ H ₅ )) gas, tetramethoxysilane (Si (OCH ₃ ) ₄ ) gas, tetraethoxysilane (Si (OC ₂₎ H _{5) 4)} gas, aminosilane gas, diaminosilanes _{(H 2 Si (NH 2)} 2) gas, triamino silanes (HSi ( NH ₂ ) ₃ ) gas, tetraaminosilane (Si (NH ₂ ) ₄ ) gas, dimethylaminosilane (H ₃ SiN (CH ₃ ) ₂ ) gas, bis (dimethylamino) silane (H ₂ Si (N (CH ₃ ) ₂ ) ₂ ) gas, tris (dimethylamino) silane (HSi (N (CH ₃ ) ₂ ) ₃ ) gas, tetrakis (dimethylamino) silane (Si (N (CH ₃ ) ₂ ) ₄ ) gas, disiloxane ((H ₃ Si) ₂ O) gas, dimethyldisiloxane ([H ₂ (CH ₃ ) Si] ₂ O) gas, tetramethyldisiloxane ([H (CH ₃ ) ₂ Si] ₂ O) gas, dimethyldimethoxydisiloxane ( [H (CH ₃ ) (CH ₃ O) Si] ₂ O) gas, tetramethoxydisiloxane ([H (CH ₃ O) ₂ Si] ₂ O) gas, tetramethyldimethoxy Sidisiloxane ([(CH ₃ ) ₂ (CH ₃ O) Si] ₂ O) gas, dimethyldiethoxydisiloxane ([H (CH ₃ ) (C ₂ H ₅ O) Si] ₂ O) gas, tetraethoxydi Siloxane ([H (C ₂ H ₅ O) ₂ Si] ₂ O) gas, disilazane ((H ₃ Si) ₂ NH) gas, dimethyldisilazane ([H ₂ (CH ₃ ) Si] ₂ NH) gas, tetra Methyldisilazane ([H (CH ₃ ) ₂ Si] ₂ NH) gas, dimethyldimethoxydisilazane ([H (CH ₃ ) (CH ₃ O) Si] ₂ NH) gas, dimethyldiethoxydisilazane ([H ( CH ₃ ) (C ₂ H ₅ O) Si] ₂ NH) gas, tetraethoxydisilazane ([H (C ₂ H ₅ O) ₂ Si] ₂ NH) gas, dimethoxytetramethyldisilazane ([(OCH ₃ A reaction gas having an alkyl group or an alkoxy group such as () (CH ₃ ) ₂ Si] ₂ NH) gas may be used. It may also be used O ₂ gas instead of steam.

(Modification 1-1)
The manufacturing process of the oxide film in the first embodiment can be changed as follows. Here, a method of forming an oxide film when shallow trench isolation (STI) is formed on the wafer 41 will be described.

  4, an oxide film 304 is embedded in a wafer 41 in which a shallow trench 301 having a depth of 600 nm to 800 nm (eg, 700 nm) and a width of 50 nm to 150 nm (eg, 100 nm) is formed (FIG. 4A), and The state where the state 303 of the oxide film 304 is removed (FIG. 4B) is shown.

  Differences from the manufacturing process of the oxide film 304 of the first embodiment are as follows.

  1. The temperature of the heater 51 of the first chamber 5 is set so that the surface temperature of the wafer 41 is 100 ° C. to 350 ° C. (for example, 300 ° C.).

  2. A silicon substrate is used as the wafer 41, and a shallow and narrow shallow trench 301 is formed by STI in a chamber (not shown) before the wafer 41 is transferred to the first chamber 5.

3. First, in a state where the pressure in the first chamber 5 is set to 133 Pa to 532 Pa (for example, 267 Pa), only dimethoxytetramethyldisiloxane gas is supplied to the first chamber 5 at a flow rate of about 75 cc / min for about 2 minutes. For the change, N ₂ gas, inert gas or water vapor gas is introduced, the pressure is once changed to about 13.3 Pa to 133 Pa (for example, 67 Pa), then returned to 133 Pa to 532 Pa (for example, 267 Pa), and a high concentration ( for example supplies 100% or a mixture of water vapor) _{O 3} gas at a flow rate of about 200 cc / min to about 2 min. The use of the RF plasma apparatus 11 is not necessary.

4). The alternating supply of dimethoxytetramethyldisiloxane gas and O ₃ gas is repeated 10 to 30 times (for example, 20 times).

  As a result, an oxide film 304 having a thickness of about 100 nm is formed on the wafer 41 as in the first embodiment. The oxide film 304 is also embedded in the shallow trench 301. However, it can be confirmed that the oxide film 304 is generated by etching with dilute hydrofluoric acid. If the state 203 exists, the reliability of element isolation is lowered, and this removal measure is essential.

  Therefore, by irradiating the wafer 41 with ultraviolet rays, carbon (C) and hydrogen (H) contained in the oxide film 304 are desorbed, so that the state 303 disappears and the oxide film in the shallow trench 301 is removed. The state of 304 is improved. The conditions for the ultraviolet irradiation treatment may be the same as in the first embodiment. In this case, the thickness of the oxide film 304 decreased by about 4% on average. When the dilute hydrofluoric acid treatment was actually performed, it was confirmed that the state 303 disappeared from the oxide film 304 in the shallow trench 301.

  As in the first embodiment, trimethoxysilane gas or the like may be used instead of the dimethoxytetramethyldisiloxane gas, and the cleaning conditions may be the same as in the first embodiment.

(Modification 1-2)
The manufacturing process of the oxide film in the modified example 1-1 can be further changed as follows.

  1. The temperature of the heater 51 of the first chamber 5 is set so that the surface temperature of the wafer 41 is 120 ° C. to 138 ° C. (for example, 130 ° C.). This temperature is around 139 ° C., which is the boiling point of the dimethoxytetramethyldisiloxane gas, but less than the boiling point. When such temperature setting is performed, the adsorption amount of the dimethoxytetramethyldisiloxane gas to the wafer 41 can be increased, and as a result, the thickness of the oxide film can be increased.

  2. A shallow trench 301 having a depth of 600 nm to 800 nm (eg, 700 nm) and a width of 50 nm to 150 nm (eg, 100 nm) is formed.

3. First, in a state where the pressure in the first chamber 5 is 133 Pa to 532 Pa (for example, 399 Pa), only dimethoxytetramethyldisiloxane gas is supplied to the first chamber 5 at a flow rate of about 75 cc / min for about 2 minutes. O ₃ gas is supplied under the same conditions as in Example 1-1. The use of the RF plasma apparatus 11 is not necessary.

4). The alternating supply of dimethoxytetramethyldisiloxane gas and O ₃ gas is repeated 5 to 15 times (for example, 10 times). Or it may steam mixed with the O ₃ gas.

  Thereafter, when the ultraviolet irradiation treatment was performed in the second chamber 6 under the same conditions as in the first embodiment, the thickness of the oxide film 304 was reduced by about 6% on average.

  As in Modification 1-1, trimethoxysilane gas or the like may be used instead of dimethoxytetramethyldisiloxane gas, but the temperature of the heater 51 of the first chamber 5 is set according to the boiling point of the alternative gas. Note the points to be set.

(Modification 1-3)
It is also possible to change the manufacturing process of the oxide film in Embodiment 1-1 as follows. Here, a method of forming an oxide film when a shallow trench is formed on the wafer 41 will be described.

  4, an oxide film 304 is embedded in a wafer 41 in which a shallow trench 301 having a depth of 600 nm to 800 nm (eg, 700 nm) and a width of 50 nm to 150 nm (eg, 100 nm) is formed (FIG. 4A), and The state where the state 303 of the oxide film 304 is removed (FIG. 4B) is shown.

  Differences from the manufacturing process of the oxide film 304 of the first embodiment are as follows.

  1. The temperature of the heater 51 of the first chamber 5 is set so that the surface temperature of the wafer 41 is 200 ° C. to 500 ° C. (for example, 300 ° C.).

  2. A silicon substrate is used as the wafer 41, and a shallow and narrow shallow trench 301 is formed by STI in a chamber (not shown) before the wafer 41 is transferred to the first chamber 5.

3. First, the shower in the first chamber 5 is modified. Specifically, dimethoxytetramethyldisiloxane gas and high-concentration O ₃ gas are prevented from being mixed in the piping and shower. The dimethoxytetramethyldisiloxane gas and the high concentration O ₃ gas are first mixed in the chamber. The water vapor may be mixed with dimethoxytetramethyldisiloxane gas in the shower, or may be mixed with O ₃ gas in the shower. With the pressure at 39.3 Pa to 532 Pa (eg, 133 Pa), dimethoxytetramethyldisiloxane gas, high concentration (eg, 100%) O ₃ gas, and water vapor gas are supplied to the first chamber 5 at about 75 cc / min, 200 cc / min, and Supply for about 7 minutes at a flow rate of 400 cc / min. Or it may be mixed O ₂ gas instead of steam gas. The use of the RF plasma apparatus 11 is not necessary.

  As a result, an oxide film 304 having a thickness of about 700 nm is formed on the wafer 41 as in the first embodiment. The oxide film 304 is also embedded in the shallow trench 301. However, it can be confirmed that the oxide film 304 is generated by etching with dilute hydrofluoric acid. If the state 203 exists, the reliability of element isolation is lowered, and this removal measure is essential.

  Therefore, by irradiating the wafer 41 with ultraviolet rays, carbon (C) and hydrogen (H) contained in the oxide film 304 are desorbed, so that the state 303 disappears and the oxide film in the shallow trench 301 is removed. The state of 304 is improved. The conditions for the ultraviolet irradiation treatment may be the same as in the first embodiment. In this case, the thickness of the oxide film 304 decreased by about 4% on average. When the dilute hydrofluoric acid treatment was actually performed, it was confirmed that the state 303 disappeared from the oxide film 304 in the shallow trench 301.

  As in the first embodiment, trimethoxysilane gas or the like may be used instead of the dimethoxytetramethyldisiloxane gas, and the cleaning conditions may be the same as in the first embodiment.

(Embodiment 2)
FIG. 5 is a schematic configuration diagram of a batch type low pressure CVD apparatus according to Embodiment 2 of the present invention. In the present embodiment, a method of processing a plurality of wafers 41 in a single process using a batch type chamber instead of the so-called cluster type chamber used in the first embodiment will be described.

FIG. 5 shows a wafer holder 214 that holds a plurality of wafers 41, a mounting table 216 for the wafer holder 214, an internal quartz tube 213 that covers the wafer holder 214, and an external quartz tube that covers the internal quartz tube 213. 212, a furnace 211 for heating the quartz tubes 212 and 213, pipes 201 to 207 for introducing O ₃ gas, trimethylsilane gas, etc. into the gas nozzle 317, a manifold 321 for gathering the pipes 201 and the like, An elevating unit 322 positioned below and elevating the mounting table 216 and a shield box 242 filled with N ₂ gas for preventing oxidation of the wafer 41 are shown.

  5 shows a state in which a gas nozzle 317 is attached between the external quartz tube 212 and the internal quartz tube 213 and gas can be supplied from the nozzle hole 318 into the internal quartz tube 213. However, the gas nozzle 317 is attached. Alternatively, the gas may be directly supplied to the internal quartz tube 213. Since a plurality of nozzle holes 318 are provided, various gases can be supplied to the wafer 41 at a uniform concentration.

  5 includes a valve 208 and a mass flow 209 provided in the pipe 201 and the like, a robot arm 241 that transports the wafer 41 to the wafer holder 214, an exhaust pump 234 that exhausts the inside of the internal quartz tube 213, and the like. An exhaust pipe 231 connecting the exhaust pump 234 and the processing chamber, a pressure gauge 232 connected to the exhaust pipe 231, and a valve 233 provided in the exhaust pipe 231 are shown.

  Here, since an opening is formed in the upper part of the internal quartz tube 213, various gases introduced into the internal quartz tube 213 pass from the internal quartz tube 213 to the external quartz tube 212 through the opening. Head. Then, the air is exhausted by the exhaust pump 234 through the space between the internal quartz tube 213 and the external quartz tube 212.

O ₂ gas, O ₃ gas, trimethylsilane gas, aminosilane (H ₃ SiNH ₂ ) gas, water vapor, He gas, and N ₂ gas pass through the pipes 201 to 207, respectively. The pipes 201 and 202 are directly connected to the nozzle 317. Therefore, O ₂ gas and O ₃ gas are introduced into the internal quartz tube 213 through the nozzle hole 318 of the nozzle 317.

  On the other hand, the pipes 203 to 207 are directly connected to the manifold 321. Therefore, trimethylsilane gas or the like is introduced into the internal quartz tube 213 through the manifold 321.

  Next, a processing procedure for the wafer 41 in which the shallow trench 301 having a depth of 600 nm to 800 nm (for example, 700 nm) and a width of 50 nm to 150 nm (for example, 100 nm) is formed using the batch type low pressure CVD apparatus shown in FIG. explain.

  First, the interior temperature of the internal quartz 213 is heated so that the set temperature of the furnace 221 is 400 ° C. to 500 ° C. (for example, 450 ° C.). In this state, the robot arm 241 is used to place the wafer 41 in which the trench is formed on the wafer holder 401 in the processing chamber.

  Here, for example, in a device having a design rule of 32 nm or less, the distance between the source region and the drain region is very narrow. Therefore, when processing exceeding 500 ° C. is performed, the source region and the drain region are physically separated. It is wise to keep the set temperature of the furnace 221 at 500 ° C. or lower because the device may not operate due to contact.

Next, the valves 208 provided in the pipes 201, 204, and 205 are opened under the control of the mass flow 209, respectively. Then, O ₂ gas is supplied to the wafer 41 through the nozzle 317 at a flow rate of 400 to 1000 cc / min (for example, 800 cc / min) and water vapor is 300 to 500 cc / min (for example, 400 cc / min), and through the manifold 321, Adjustment is made so that aminosilane gas is supplied to the wafer 41 at a flow rate of 100 to 300 cc / min (for example, 200 cc / min).

  At this time, the valve 233 is opened and the processing chamber is evacuated by the exhaust pump 234 under the condition that the pressure gauge 232 becomes 67 Pa to 267 Pa (for example, 133 Pa).

The supply time of each gas is about 1 hour to 1 and a half hours (eg, 70 minutes). According to the above method, the aminosilane gas, water vapor and O ₂ gas can be allowed to react slowly, so that a thick oxide film can be formed at a relatively low temperature. As a result, an oxide film having a thickness of 700 nm is formed on each wafer 41.

Thereafter, the oxide film was annealed at 400 ° C. to 500 ° C. (for example, 450 ° C.) for about 30 minutes in the O ₃ gas atmosphere in the first chamber 5 or using the second chamber 6. The state that existed in the oxide film in the trench had disappeared.

In place of aminosilane gas, diaminosilane (H ₂ Si (NH ₂ ) ₂ ) gas, triaminosilane (HSi (NH ₂ ) ₃ ) gas, tetraaminosilane (Si (NH ₂ ) ₄ ) gas, or dimethylaminosilane (H ₃ SiN (CH ₃ ) ₂ ) gas, bis (dimethylamino) silane (H ₂ Si (N (CH ₃ ) ₂ ) ₂ ) gas, tris (dimethylamino) silane (HSi (N (CH ₃ ) ₂ ) ₃ ) gas, tetrakis (dimethylamino) silane (Si (N (CH ₃ ) ₂ ) ₄ ) gas, disiloxane ((H ₃ Si) ₂ O) gas, dimethoxytetramethyldisilazane ([(OCH ₃ ) (CH _{3) 2 Si] 2} NH) may use other silicon-based gas such as a gas.

Further, O ₂ gas is set to 400 cc / min to 1000 cc / min (for example, 800 cc / min), and diborane (B ₂ H ₆ ) gas as an additive or phosphine (PH ₃ ) gas having a concentration of 10% is set to 50 cc / min. The oxide film may be deposited for about 1 hour at a pressure of about 133 Pa without changing other gas conditions of min to 200 cc / min (for example, 100 cc / min). The cleaning conditions in the processing chamber may be the same as in the first embodiment, and cleaning may be performed using NF ₃ gas, Ar gas, or the like excited through a cleaning gas pipe (not shown).

(Modification 2-1)
It is also possible to change the manufacturing process of the oxide film in Embodiment 2 as follows.

  1. A shallow trench having a depth of 600 nm to 800 nm (for example, 700 nm) and a width of 50 nm to 150 nm (for example, 100 nm) is formed.

2. Instead of aminosilane gas, tetramethoxysiloxane (H (OCH ₃ ) ₂ Si—O—SiH (OCH ₃ ) ₂ ) gas is allowed to flow through the pipe 204.

3. Through the nozzle 317, O ₂ gas is supplied to the wafer 41 at a flow rate of 400 to 1000 cc / min (for example, 800 cc / min), and tetramethoxysiloxane is supplied to the wafer 41 through the manifold 321 to 100 to 300 cc / min (for example, 200 cc / min). min) so that the flow rate is supplied. In addition, water vapor may be supplied at a flow rate of 100 cc / min to 200 cc / min (for example, 100 cc / min).

In this way, the tetramethoxysiloxane gas reacts with the O ₂ gas by the reaction of SiH ₄ gas and the like with the O ₂ gas (H and O ₂ in the tetramethoxysiloxane gas react), and the low temperature deposition at 500 ° C. or lower. Can be made possible.

  As a result, an oxide film having a thickness of 700 nm is formed on the wafer 41. Thereafter, when the wafer 41 taken out from the wafer holder 214 was subjected to an ultraviolet irradiation process under the same conditions as in the second embodiment, the oxide film disappeared. Moreover, the thickness of the oxide film decreased by about 4% on average. Further, a dimethoxysiloxane gas or the like may be used instead of the tetramethoxysiloxane gas. The cleaning conditions may be the same as in the second embodiment.

(Modification 2-2)
It is also possible to change the manufacturing process of the oxide film in Embodiment 2 as follows. The gas used here is the same as in Modification 1-1. The differences from the oxide film manufacturing process of the second embodiment are as follows.

  1. The temperature of the heater 211 of the batch type low pressure CVD apparatus in FIG. 5 is set so that the surface temperature of the wafer 41 is 120 ° C. to 138 ° C. (for example, 130 ° C.). This temperature is around 139 ° C., which is the boiling point of the dimethoxytetramethyldisiloxane gas, but less than the boiling point. When such temperature setting is performed, the adsorption amount of the dimethoxytetramethyldisiloxane gas to the wafer 41 can be increased.

  2. A shallow trench having a depth of 600 nm to 800 nm (for example, 700 nm) and a width of 50 nm to 150 nm (for example, 100 nm) is formed.

3. First, in a state where the pressure in the first chamber 5 is set to 133 Pa to 532 Pa (for example, 399 Pa), only dimethoxytetramethyldisiloxane gas is supplied to the first chamber 5 at a flow rate of about 200 cc / min for about 2 minutes. For the change, N ₂ gas, inert gas or water vapor gas is introduced, the pressure is temporarily changed to about 13.3 Pa to 133 Pa (for example, 67 Pa), then returned to 133 Pa to 532 Pa (for example, 399 Pa), and a high concentration ( for example supplying 100% or a mixture of water vapor) _{O 3} gas at a flow rate of about 400 cc / min to about 2 min.

4). The alternate supply of dimethoxytetramethyldisiloxane gas and O ₃ gas is repeated 50 to 100 times (for example, 70 times).

  As a result, an oxide film having a thickness of 700 nm is formed on the wafer 41. Thereafter, when the wafer 41 taken out from the wafer holder 214 was subjected to an ultraviolet irradiation process under the same conditions as in the second embodiment, the oxide film disappeared. Moreover, the thickness of the oxide film decreased by about 7% on average.

When the annealing process is performed in the second chamber 6, for example, the low pressure mercury lamp 101 is used at 400 ° C., and the wafer 401 may be irradiated with low pressure mercury light having a power of 10 mW / cm ^{2 in} an O ₂ atmosphere. .

  Further, similarly to the modified example 1-1, trimethoxysilane gas or the like may be used instead of the dimethoxytetramethyldisiloxane gas, but the temperature of the heater 51 of the first chamber 5 is set according to the boiling point of the alternative gas. Note the points to be set. The cleaning conditions may be the same as in the second embodiment.

(Modification 2-3)
It is also possible to change the manufacturing process of the oxide film in Embodiment 2 as follows.

  1. A shallow trench having a depth of 600 nm to 800 nm (for example, 700 nm) and a width of 50 nm to 150 nm (for example, 100 nm) is formed.

2. The additive flowing through the pipe 203 is changed to silane (SiH ₄ ) gas or disilane (Si ₂ H ₆ ) gas. Further, instead of aminosilane gas, trimethoxysilane (HSi (OCH ₃ ) ₃ ) gas is allowed to flow through the pipe 204.

3. Through the nozzle 317, O ₂ gas is supplied to the wafer 41 at a flow rate of 400 to 1000 cc / min (eg, 800 cc / min), SiH ₄ gas, etc., at a flow rate of 50 to 150 cc / min (eg, 100 cc / min), and through the manifold 321. The wafer 41 is adjusted so that trimethoxysilane is supplied at a flow rate of 100 to 300 cc / min (for example, 200 cc / min). In addition, water vapor may be supplied at a flow rate of 100 cc / min to 200 cc / min (for example, 100 cc / min).

By doing so, the trimethoxysilane gas easily reacts with the O ₂ gas due to the reaction between the SiH ₄ gas and the O ₂ gas, and the low temperature decomposition of the SiH ₄ gas and the like enables the low temperature deposition at 450 ° C. or less. .

As a result, an oxide film having a thickness of 700 nm is formed on the wafer 41. Thereafter, when the wafer 41 taken out from the wafer holder 214 was subjected to an ultraviolet irradiation process under the same conditions as in the second embodiment, the oxide film disappeared. Moreover, the thickness of the oxide film decreased by about 4% on average. Further, triethoxysilane gas or the like may be used instead of trimethoxysilane gas.
Further, Si ₂ H ₆ gas may be used instead of SiH ₄ gas. The cleaning conditions may be the same as in the second embodiment.

  A semiconductor device manufactured using the semiconductor manufacturing apparatus described in Embodiment 1 or the like can be suitably used for a display device such as liquid crystal, plasma, and EL (electroluminescence). In addition, imaging devices such as digital cameras and digital still cameras, image forming devices such as facsimiles, printers, and scanners, optical devices such as CLC elements and light emitting laser devices, communication devices such as mobile phones, personal computers, etc. Any glass substrate for forming an element of an electronic component or the like, such as a memory built in the information processing apparatus or a removable memory, can be preferably used.

Finally, the gas that can be preferably used in each embodiment and modification is summarized in a table. In the table, the low temperature is a temperature of 300 ° C. or lower, and the intermediate temperature is a temperature of 300 ° C. or higher and 500 ° C. or lower.

Claims (10)

Means for supplying a silane-based gas, a siloxane-based gas, or a silazane-based gas containing at least one selected from an alkyl group, an alkoxy group, and an amino group;
Means for supplying an oxidant;
An apparatus for manufacturing a semiconductor device, comprising means for reacting the gas and an oxidant under reduced pressure at a temperature of 500 ° C. or lower.   The semiconductor device manufacturing apparatus according to claim 1, further comprising means for reacting in a plasma state at a temperature of 400 ° C. or lower.   The semiconductor device manufacturing apparatus according to claim 1, further comprising means for supplying an additive selected from silane gas, disilane gas, phosphorus-based gas, or boron-based gas.   The semiconductor device manufacturing apparatus according to claim 1, further comprising means for performing an annealing process using ozone gas or ultraviolet irradiation after the reaction.   Furthermore, the manufacturing apparatus of the semiconductor device in any one of Claims 1-4 provided with a means to dilute an oxidizing agent with an inert gas. Introducing a silane-based gas, siloxane-based gas, or silazane-based gas containing at least one selected from an alkyl group, an alkoxy group, and an amino group onto a substrate heated to the boiling point of these gases or less (A);
A step (B) of introducing an oxidant and reacting with the gas under a reduced pressure at a temperature of 500 ° C. or lower.   The semiconductor according to claim 6, wherein the temperature of the step (B) is a temperature not higher than the boiling point of a silane-based gas, a siloxane-based gas, or a silazane-based gas containing at least one selected from an alkyl group, an alkoxy group, and an amino group. Device manufacturing method.   The semiconductor device production according to claim 6, wherein the silane-based gas, siloxane-based gas, or silazane-based gas containing at least one selected from an alkyl group, an alkoxy group, and an amino group comprises a compound having at least one H group. Method. The method for manufacturing a semiconductor device according to claim 6, wherein the oxidizing agent is at least one selected from O ₂ , H ₂ O, and O ₃ .   A semiconductor device whose design rule is 32 nm or less, and in which the source region and the drain region are not in physical contact.