This invention relates to a method for producing silicon nitride films and to a process for fabricating semiconductor devices using said method.
When the fabrication of silicon nitride film is carried out by the generally known low-pressure chemical vapor deposition (LPCVD) procedure using ammonia (NH3) and a silicon source such as dichlorosilane (SiH2Cl2), tetrachlorosilane (SiCl4), or hexachlorodisilane (Si2Cl6), a substantial deterioration in leakage characteristics and wet etching resistance is noted when the film production temperature declines below, for example, 600° C. It is thought that the generation of silicon-nitrogen bonds by reaction between the silicon source and nitrogen source is not promoted in such a low-temperature film-formation process and that the resulting occurrence of a large number of silicon dangling bonds in the silicon nitride film causes the deterioration in film quality.
The use of monomethylamine (CH3NH2) as nitrogen source in place of ammonia (NH3) is described in, for example, Nonpatent Reference 1, with the goal of improving silicon nitride film quality. This article concerns an evaluation of silicon nitride film formation at 600-800° C. by hot-filament CVD and thermal CVD using monosilane (SiH4) as the silicon source and monomethylamine (CH3NH2) as the nitrogen source.
Monomethylamine (CH3NH2) was selected for the nitrogen source in this study because the decomposition energy of monomethylamine (CH3NH2) is, at 3.4 eV (CH3NH2), less than the 4.48 eV (NH2—H) of ammonia (NH3). The result was a reduction in the hydrogen concentration in the film to ≦1×1021 cm−3 at a film-formation temperature of 600° C.
Patent Reference 1 describes a method for forming silicon nitride films at 400-650° C. by LPCVD using trimethylamine ((CH3)3N, an amine-type gas) for the nitrogen source and a silane-type gas. However, this method requires that the trimethylamine ((CH3)3N) be preheated to 500-700° C. due to its high heat capacity. It is also stated that an insufficiently nitridated silicon nitride film (refractive index: RI=2.9) is obtained when silicon nitride film production is carried out, for example, at 550° C., without this preheating.
[Nonpatent Reference 1]
Yasui et al., Appl. Phys. Lett. 56(10), 5 Mar. 1990, p. 898-900, “Amorphous SiN films grown by hot-filament chemical vapor deposition using monomethylamine”.
[Patent Reference 1]
Japanese Laid Open (Unexamined or Kokai or A) Patent Application Number 2002-009072.
The silicon nitride films produced by LPCVD exhibit a very good coverage ratio and are broadly utilized in the fabrication of transistors (MOSFETs, etc.). However, their film properties undergo deterioration (deterioration in leakage properties, increase in impurities, etc.) when their production temperature is lowered for the purpose of reducing the thermal effects on the semiconductor device.
For example, when low-temperature silicon nitride film is produced by LPCVD using ammonia (NH3) and a silicon source such as hexachlorodisilane (Si2Cl6), the lower film-fabrication temperatures are accompanied by a deterioration in leakage properties, a deterioration in the wet etching resistance, and a substantial increase in the levels of hydrogen (H) and chlorine (Cl) in the film. It is thought that the generation of silicon-nitrogen bonds by reaction between the silicon source and nitrogen source is not promoted in the low-temperature film-formation process (for example, ≦600° C.) and that the resulting presence of a large number of silicon dangling bonds in the silicon nitride film is a cause of the deterioration in film quality.
In order to realize even lower thermal budgets when silicon nitride film is used for the sidewall film formed on the sidewall of the gate electrode of a semiconductor device or is used as the liner film elaborated prior to production of the interlayer dielectric film, a method is required that can produce high-quality silicon nitride film at high coverage ratios at film-formation temperatures ≦500° C., for example, at 450° C. However, issues with regard to a reduced electrical reliability by the semiconductor device are created by the deterioration in leakage characteristics and other problems that accompany lower film-formation temperatures.
Silicon nitride film production at a film-formation temperature ≦600° C. is not accomplished in Nonpatent Reference 1. With regard to Patent Reference 1, due to the use of trimethylamine the required film properties cannot be obtained without preheating the gas.
The object of this invention, therefore, is to improve the properties of low-temperature LPCVD silicon nitride films by improving, inter alia, their leakage properties and wet etch resistance by terminating the silicon dangling bonds present in low-temperature (450-600° C.) silicon nitride films with carbon that carries a carbon-hydrogen bond.
The present invention is characterized by the use for the formation of low-temperature silicon nitride film by LPCVD of ammonia (NH3) as nitrogen source, monomethylamine (CH3NH2) as the C—H bond-containing source, and Si-containing gas (e.g., monosilane (SiH4), disilane (Si2H6), dichlorosilane (SiH2Cl2), tetrachlorosilane (SiC4), hexachlorodisilane (Si2Cl6)) as silicon source. Disilazane ((SiH3)2NH) can also be used as a silicon source. When disilazane is used, it can be utilized not only for silicon, but also as a portion of the nitrogen source. Hydrazine (N2H4) can also be used as a nitrogen source.
The reason for the use of monomethylamine (CH3NH2) as the C—H bond-containing source in the aforementioned fabrication of silicon nitride film is that the 3.4 eV bond energy of monomethylamine (CH3NH2), being less than the 4.48 eV bond energy of the ammonia (NH2—H) used as the nitrogen source, enables degradation of the CH3—NH2 bond to occur to a satisfactory degree even at low temperatures. This enables the production of methyl (CH3) that will terminate the silicon dangling bonds.
Gas other than monomethylamine (CH3NH2) that contains methyl in the source substance can be used, such as dimethylamine ((CH3)2(NH)) and trimethylamine ((CH3)3N). It is also possible to use gas that contains a non-methyl alkyl group such as ethyl, propyl, butyl, and so forth.
This invention relates to a method for forming silicon nitride films and to a process for fabricating semiconductor devices using this method, as indicated in the following (1) to (18) which are described by claims 1 to 18.
(1) Method for forming silicon nitride film, that is characterized by the use of gas (monosilane, disilane, dichlorosilane, tetrachlorosilane, hexachlorodisilane, disilazane, etc.) that contains at least silicon in the source substance as silicon source and gas (ammonia, hydrazine, etc.) that contains at least nitrogen in the source substance as nitrogen source and by the additional use of gas that contains at least the carbon-hydrogen bond in the source substance.
(2) Method for forming silicon nitride film, characterized by the use of gas (monosilane, disilane, dichlorosilane, tetrachlorosilane, hexachlorodisilane, disilazane, etc.) that contains at least silicon in the source substance as silicon source and gas (ammonia, hydrazine, etc.) that contains at least nitrogen in the source substance as nitrogen source and by the additional use of gas that contains at least the methyl group in the source substance.
(3) Method for forming silicon nitride film, characterized by the use of gas that contains at least silicon in the source substance as silicon source and gas that contains at least nitrogen in the source substance as nitrogen source and by the additional use of gas that contains at least an alkyl group (methyl, ethyl, propyl, butyl, etc.) in the source substance.
(4) Method for forming silicon nitride film, characterized by the use in the aforementioned (1)-(3) of gas that contains at least nitrogen and methyl in the source substance as nitrogen source.
(5) Method for forming silicon nitride film, characterized by the use in the aforementioned (1)-(3) of gas that contains at least nitrogen and alkyl (e.g., methyl, ethyl, propyl, butyl) in the source substance as nitrogen source.
(6) Method for forming silicon nitride film, characterized by the use of gas that contains at least nitrogen and methyl in the source substance as the gas described in (1) that contains at least the carbon-hydrogen bond in the source substance.
(7) Method for forming silicon nitride film, characterized by the use of gas that contains at least nitrogen and alkyl in the source substance as the gas described in (1) that contains at least the carbon-hydrogen bond in the source substance.
(8) Method for forming silicon nitride film, characterized by the use of gas that contains at least methylamine in the source substance as the gas described in (1) that contains at least the carbon-hydrogen bond in the source substance.
(9) Method for forming silicon nitride film, characterized in that the silicon nitride film formation described in (1)-(8) is carried out by low-pressure CVD.
(10) Method for forming silicon nitride film, characterized in that, when film formation is carried out using the source substances described in (1)-(5) to give silicon nitride film containing 0.7-1.3 nitrogen where the silicon component is designated as 1, said silicon nitride film contains 0.1-0.6 carbon.
(11) Method for forming silicon nitride film, characterized by the use of chlorine- and silicon-containing gas comprising dichlorosilane, tetrachlorosilane, or hexachlorodisilane as the silicon source described in (1) and the use of methyl- and nitrogen-containing gas comprising monomethylamine, dimethylamine, or trimethylamine as nitrogen source.
(12) Process for fabricating a semiconductor device in which a source region and a drain region separated by a gap are formed in a semiconductor substrate, a gate electrode is formed above the channel region that is formed in the gap between the source region and drain region wherein the gate electrode is separated from the channel region by a gate dielectric film, a source electrode is formed on the source region, a drain electrode is formed on the drain region, and sidewall film comprising silicon nitride film is formed on the sidewalls of the gate dielectric film and gate electrode, said method being characterized by the use for formation of the sidewall film comprising silicon nitride of gas that contains at least silicon in the source substance as silicon source and gas that contains at least nitrogen in the source substance as nitrogen source and by the additional use of gas that contains at least the carbon-hydrogen bond.
(13) Process for fabricating a semiconductor device that characteristically uses low-pressure CVD for formation of the silicon nitride film as described in (12) wherein the silicon nitride film formation temperature is at least 450° C. but no more than 600° C.
(14) Process for fabricating a semiconductor device, characterized by the use of a metal silicide film for the source electrode and drain electrode described in (12).
(15) Process for fabricating a semiconductor device, characterized in that, after formation of the metal silicide film described in (14), a liner film comprising silicon nitride film is formed on the entire surface containing this metal silicide film and the gate electrode, wherein said liner film comprising silicon nitride film is produced using low-pressure CVD, gas that contains at least chlorine and silicon in the source substance as silicon source, and gas that contains at least methyl and nitrogen in the source substance as nitrogen source.
(16) Process for fabricating a semiconductor device that characteristically uses low-pressure CVD for formation of the silicon nitride film as described in (15) wherein the liner film comprising silicon nitride film is formed at a temperature of at least 450° C. but no more than 600° C.
(17) Process for fabricating a semiconductor device, characterized in that, after formation of the liner film comprising silicon nitride film as described in (15), an interlayer dielectric film is formed on the liner film; the interlayer dielectric film is selectively etched over the gate electrode, source electrode, and drain electrode; and metal is filled into the etched regions.
(18) Process for fabricating a semiconductor device, characterized by elaborating metal interconnects on the interlayer dielectric film after metal has been filled into the etched regions as described in (17) wherein the metal interconnects are connected with the metal fill.
The present invention carries out silicon nitride film formation at low temperatures and thereby enables a reduction in the thermal budget from that imposed by the prior-art high-temperature production of silicon nitride films for semiconductor devices such as MOSFETs. In addition, by providing silicon nitride film with improved film properties, this invention provides improved reliability for the electrical properties of semiconductor devices such as MOSFETs.
As a particular matter, application of this invention to the sidewalls of a semiconductor device such as a MOSFET can improve the leakage characteristics for this sidewall and can suppress impurity diffusion into the gate dielectric film and gate electrode encompassed by the sidewall. This results in stabilization of the electrical properties of the semiconductor device, e.g., a MOSFET.
Embodiments of the present invention are described in the following with reference to examples.
The addition of the monomethylamine makes it possible to terminate the silicon dangling bonds with the methyl group and thereby enables an improvement in the film quality and leakage characteristics, etc., even at low temperatures (450-600° C.). While low temperatures (450-600° C.) are identified for the film-formation temperature, the film-formation temperature is not limited to these temperatures. That is silicon nitride film with good film properties and good leakage characteristics can be obtained even at film-formation temperatures below 450° C.
In specific terms, a silicon nitride film is formed on the silicon wafer 14 mounted in the boat 13 by the feed of a silicon source (Si2Cl6) from the injector 11 and the feed of a nitrogen source (CH3NH2+NH3) from the injector 12 into the LPCVD tool 10.
The film-formation conditions here can be exemplified as follows: temperature=525° C. (midpoint temperature in the low-temperature range of 450-600° C.), pressure=1 torr, Si2Cl6 flow rate=2 cc, CH3NH2 flow rate=3 cc, and NH3 flow rate=17 cc. The film properties of the silicon nitride film can as a consequence be improved due to the highly efficient reaction of the CH3NH2 and Si2Cl6, which are thoroughly decomposed at the film-formation temperature of 525° C. The film-formation conditions are not limited to the preceding, and, for example, temperatures of 450-600° C., pressures of about 0.2-5 torr, and gas flow rate ratios (Si2Cl6 flow rate/(CH3NH2+NH3 flow rate)) of about 1/10 to 1/100 are desirable.
This low-temperature film formation provides increased device reliability because it provides an improved silicon nitride film quality without the application of excess heat to the semiconductor device during the device fabrication process.
Examples of the improved film quality are illustrated in
This comparative evaluation shows that 15% monomethylamine (CH3NH2) provided less H2O desorption than for the heretofore used 100% ammonia (NH3) (0% for the monomethylamine ratio (CH3NH2/(CH3NH2+NH3)), while 25% monomethylamine (CH3NH2) provided more H2O desorption.
Therefore, in connection with the range shown in
In similar fashion to
Therefore, in connection with the range shown in
Therefore, considering
When silicon nitride film was produced under the conditions specified for Example 1, a substantial improvement in film quality was obtained for 5-20% monomethylamine (CH3NH2) in the nitrogen source. When plotted against the concentration of carbon incorporated into the silicon nitride film, this range corresponds to 10-15% carbon in the film composition as shown in
It is thought that a primary factor for the improvement in film quality seen in
FIGS. 8(a) through (d) contain process cross sections that illustrate an example of the application of the inventive silicon nitride film to a MOSFET (dielectric gate transistor).
As shown in
A channel region 75 is formed between the SD extensions in this MOSFET 70, while a sidewall film 78 is formed on the sidewall surfaces of the gate dielectric film 76 and gate electrode 77. This sidewall film 78 comprises Si3N4 film and is formed using the LPCVD tool shown in
The gate dielectric film under consideration frequently has a two-layer structure in which the lower layer is SiO2 film and the upper layer is formed of a high-k film such as HfO2. The inventive silicon nitride film may be used for the lower film in these cases. A trilayer film may also be used in which the lower layer is SiO2 film, the middle layer is the silicon nitride film, and the upper layer is a high-k film.
A polysilicon film, for example, is then formed on the source region 74a and the drain region 74b as shown in
Then, as shown in
As shown in
While low-pressure CVD is preferred for production of the aforementioned silicon nitride film, the subject silicon nitride film can be produced by atmospheric pressure CVD or by some other technique such as, for example, plasma CVD or catalytic CVD.
Due to the addition in Example 2 of monomethylamine (CH3NH2) to the film-formation source substances used for fabrication of the silicon nitride sidewall film, the lateral leakage at the prior-art sidewall 88 shown in
While Example 2 employed the addition of monomethylamine to the silicon and nitrogen sources in the production of the sidewall and liner films in a MOSFET, this addition can also be used with the dielectric films in SOI structures and the protective films on the device surface.
Number | Date | Country | Kind |
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JP 2003-428942 | Dec 2003 | JP | national |
JP2004-338459 | Nov 2004 | JP | national |