1. Field of the Invention
The present invention relates to a method for forming an insulating film in a semiconductor device, and particularly relates to a method for forming a gate insulating film in a MIS (Metal Insulator Semiconductor) transistor or a capacitor insulating film in a MIM (Metal Insulator Metal) capacitor.
2. Description of the Related Art
In recent years, with the increase in integration of semiconductors, metal oxides and the like (high-k films) which have a large dielectric constant have been in use for insulating films of the semiconductors. For example, Al2O3, HfO2 and the like are known as the high-k films, and an ALD (Atomic Layer Deposition) method is used as a technique for forming the high-k film. In this ALD method, trimethyl aluminum [TMA: Al(CH3)3] and water vapor (H2O) are for example used as precursor, and these precursor are alternately sprayed onto an Si substrate to form an Al2O3 film. At this time, a CH3 group (methyl group) constituting the precursor is captured in the film and behaves as impurities (CxHy) to cause deterioration in film quality. As a method for removing the impurities, for example in the case of a gate insulating film in a MIS transistor, typically, a high-k film 52 having been formed on the upper surface of a Si substrate 51 is heat treated, as shown on the right side of
However, the heat treatment after the film formation as thus described is not sufficient, only removing the impurities 53 in the vicinity of the surface of the formed high-k film 52 as shown in
There is another impurity removing method other than the above-mentioned heat treatment, in which plasma oxidation is performed for the removal, as described in “Hitachi Kokusai Electric Inc, Extended Abstracts of 49th Spring Meeting of Japan Society of Applied Physics, 28p-A-11-14”. This impurity removing method comprises a step of forming HfO2 (hafnium oxide) film by CVD (Chemical Vapor Deposition) method in combination with a step of removing impurities by plasma oxidation. However, there is a problem even with this method in that the interface layer 54 as shown in
The foregoing problems have occurred not only in forming the gate insulating film of the MIS transistor, but similarly in forming a capacitor insulating film of a MIM capacitor.
This invention was made, taking note of the foregoing matters, and has an object to provide a method for forming an insulating film in a semiconductor device (hereinafter simply referred to as an insulating film forming method), capable of preventing as many impurities as possible, which cause deterioration in film quality, from existing in an insulating film in a semiconductor device.
In order to achieve the above-mentioned object, an insulating film forming method of the present invention is characterized in that a step of forming an insulating film so as to have a thickness in the range of 0.3 to 2 nm and a step of removing impurities from the insulating film are repeated a plurality of times, to form an insulating film having a prescribed thickness (claim 1).
In the insulating film forming method according to claim 1, an insulating film having a required thickness is not formed in a single process, but the step of forming an insulating film so as to have a thickness in the range of 0.3 to 2 nm and the step of removing impurities from the insulating film are repeated a plurality of times to form an insulating film having a prescribed thickness. In this manner, it is possible to easily and certainly form a high-k film containing as few impurities as possible, while preventing inconvenience caused by the growth of the interface layer.
The step of removing impurities may be performed in a reducing gas atmosphere or an oxidizing gas atmosphere (claim 2), and further, the step of removing impurities may be performed in a reducing gas atmosphere combined with an oxidizing gas atmosphere (claim 3). It is possible to easily and certainly form a desired high-k film in any of the gas atmospheres.
The reducing atmosphere in the step of removing impurities can be formed of any of single gases of an ammonia gas, a hydrogen gas and an inert gas, a mixed gas of these gases or plasma nitrogen, or formed in a vacuum (claim 4).
Further, the oxidizing gas atmosphere in the step of removing impurities can be formed of any of single gases of an oxygen gas, a nitrogen monoxide gas, a nitrous oxide gas and an ozone gas, a mixed gas of these gases or plasma oxygen (claim 5).
In the following, the present invention is specifically described with respect to drawings. First,
Reference numeral 5 denotes a gate electrode to be formed on the upper surface of the gate insulating film 4. For example, the gate electrode 5 is made of a noble metal such as Pt (platinum) or a high melting point metal such as TiN or TaN, the noble metal and the high melting point metal not reacting with a polycrystal Si film, a polycrystal SiGe film or the gate insulating film 4. Reference numeral 6 denotes a channel region. P (phosphorous) or the like is injected into an n channel and B (boron) or the like is injected into a p channel, and those channels are heat treated at temperatures of 800 to 1,000° C. for 10 to 30 minutes to be activated. Reference numeral 7 denotes an interlayer insulating film, which for example comprises SiO2 or the like and is formed by CVD (Chemical Vapor Deposition) method or the like. Reference numeral 8 denotes an extraction electrode of the channel 6. The extraction electrode 8 for example comprises Al and serves as a source/drain electrode. It is to be noted that patterning is performed for example by means of the photolithography technique.
The gate insulating film 4 is made of a high-k film having a required thickness. As shown in
First, for example, on a Si substrate made of a Si monocrystal plate having an appropriate thickness (e.g. about 500 μm), an Al2O3 film was formed by the ALD method so as to have a thickness of 0.3 to 6.3 nm. The film was formed under conditions that a substrate temperature was 250° C. and as precursor, TMA (Al(CH3)3: trimethyl aluminum) was used as an Al precursor while a water vapor gas was used as an oxidant. The Al2O3 film was analyzed using a TDS (Thermal Desorption Spectroscopy) device.
Since TDS is a method of increasing a gas temperature and simultaneously analyzing a gas being desorbed, performing TDS can be considered as being equivalent to performing heat treatment. From the results of this analysis, it was discovered that the thickness of the film from which impurities can be removed by heat treatment is limited to about 1.5 nm or smaller, and impurities may remain in a film having a thickness exceeding this limitation.
Further, for example, on a Si substrate made of a Si monocrystal plate having an appropriate thickness (e.g. about 500 μm), an HfO2 film was formed by the ALD method so as to have a thickness of 0.7 to 7.5 nm. The film was formed under conditions that a substrate temperature was 250° C. and as the precursor, TDMAH (Hf(N(CH3)2)4:tetrakis(dimethylamino) hafnium) was used as an Hf precursor while the water vapor gas was used as the oxidant. The HfO2 film was subjected to TDS using the TDS device.
Moreover, for example, on a Si substrate made of a Si monocrystal plate having an appropriate thickness (e.g. about 500 μm), an HfAlOx film was formed by the ALD method so as to have a thickness of 0.7 to 11 nm. The film was formed under conditions that a substrate temperature was 250° C. and as the precursor, TMA was used as an Al precursor and TDMAH was used as the Hf precursor while the water vapor gas was used as the oxidant. The HfAlOx film was subjected to TDS using the TDS device.
From the results shown in
It is then derived from the results shown in FIGS. 2 to 4 that the thickness of the film from which impurities can be removed changes depending upon the kind of element to constitute the film, and that the impurities can be certainly removed by heat treatment when the film thickness is in the range of 0.3 to 2.0 nm (optimally in the range of 0.5 to 1.8 nm). It should be noted that 0.3 nm is a minimum film thickness for forming a film, and it corresponds to a thickness of one monolayer (monoatomic layer).
Next, the impurity removing step (anneal step) to be performed after the film forming method is described. This impurity removing step (anneal step) is to anneal a high-k film in an atmosphere of a certain gas in a prescribed temperature condition. As the atmosphere gas, a reducing gas atmosphere or an oxidizing gas atmosphere can be employed. After the film forming step, the impurity removing step (anneal step) is performed in the reducing gas atmosphere appropriately combined with the oxidizing gas atmosphere.
Next described is the insulating film forming method of the present invention, and more specifically, a concrete example of the method for forming the gate insulating film 4 of the MIS transistor 1.
Subsequently, the HfAlOx film is heat treated in an NH3 (ammonia) gas atmosphere as the reducing gas atmosphere at 650° C. for 30 seconds, to treat impurities (first heat treatment, c.f. reference numeral 12 in
After the first heat treatment has performed, an HfAlOx film is formed so as to have the same thickness under the same film formation conditions as in the case of the first film formation. (second film formation, c.f. reference numeral 11 in
After the second film formation has performed, heat treatment is performed in an oxygen gas atmosphere (e.g. under a pressure of 130 Pa) at the same temperature for the same period of time as in the case of first heat treatment (second heat treatment, c.f. reference numeral 12 in
Thereafter, the film formation and the heat treatment are alternately repeated until the seventh film formation and the seventh heat treatment are completed. Here, the heat treatment is performed in the same manner as in the second heat treatment.
The eighth film formation is performed in the same manner as in the first to seventh film formations, whereafter the impurities are treated by heat treatment in the oxygen gas atmosphere (oxidizing gas atmosphere) at the same temperature and for the same period of time as in the case of the first to seventh heat treatments, to treat the impurities.
In
It was also confirmed that, in the case of the HfAlOx film according to the method of the present invention, there formed no interface layer having a low dielectric constant on the interface with Si.
As thus described, the HfalOx film (high-k film) according to the method of the present invention contains few impurities, and there is no low dielectric constant layer between the HfalOx film and Si. Further, in the method of the present invention, since the impurities can be removed at a relatively low temperature of 650° C., crystallization of the high-k film is favorably suppressed, thereby eliminating disadvantages of crystallization of the high-k film, i.e. once crystallized, the high-k film has a crystal grain boundary as a point of weakness, resulting in decreased reliability.
Next,
Among the samples A to C showing the high-k films according to the method of the present invention, the samples A and B are in an ammonia gas atmosphere in a first anneal (heat treatment) whereas the sample C is annealed in the oxygen gas atmosphere in the first anneal (heat treatment). Moreover, in second and third anneals, the samples A is annealed in the ammonia gas atmosphere whereas the sample B is annealed in the oxygen gas atmosphere. Meanwhile, the sample C is annealed in the oxygen gas atmosphere in the first through third anneals (heat treatments) The physical properties of the foregoing samples A to D were evaluated. Namely, an amount of carbon as residual impurities in the film was analyzed by SIMS (Secondary Ionization Mass Spectrometer). Further, the samples were subjected to the x-ray reflectance measurement to obtain the denseness thereof. The results of the analysis and the measurement were shown in Table 1 below:
It is found from the results of Table 1 above that impurities can be removed from the samples A to C according to the method of the present invention, and that these samples are dense. Further, a sample, having been treated with plasma oxide at 200 W throughout the impurity removing step, contains carbon in an amount of 0.18, revealing that impurities are removable also by the plasma oxide treatment.
Furthermore, as the electric characteristics of each of the above-mentioned samples A to D, hysteresis (relation between an applied voltage and capacity) in a CV (Capacitance-Voltage) curve and a leak current were measured, to obtain the results as shown in
It is found from the above table 2 that, any of the samples A to C according to the method of the present invention is more excellent in electric characteristic than the sample D according to the conventional method. Namely, the smaller a hysteresis in a CV curve of a film, the lower the interface level of the film and the better quality the film has. The hysteresis of each of the samples A to C is significantly smaller than that of Sample D. Further, the leak current of each of the samples A to C is significantly smaller than that of the sample D. This is because, as apparent from
In each of the foregoing examples, the reducing gas atmosphere or the oxidizing gas atmosphere was employed as the gas atmosphere in the impurity removing step (heat treatment or anneal step), and the ammonia gas was used as the reducing gas atmosphere while the oxygen gas was used as the oxidizing gas atmosphere. However, the present invention is not limited to those gases and various kinds of gases can be employed. Namely, the reducing gas atmosphere in the impurity removing step may be formed by the use of a hydrogen gas or an inert gas, by the use of a mixed gas of the ammonia gas, the hydrogen gas or the inert gas, or by the use of plasma nitrogen, or may further be formed in a vacuum. Moreover, the oxidizing gas atmosphere in the impurity removing step may be formed by the use of a nitrous oxide (NO), a nitrogen monoxide (N2O) gas, or an ozone gas, or by the use of a mixed gas obtained by appropriately mixing these gases, or further by the use of plasma oxygen.
Any of the foregoing embodiments was application of the method of the present invention to the method for forming the gate insulating film 4 of the MIS transistor 1, and the method for forming the gate insulating film 4 made of a high-k film on the Si substrate 2. However, the present invention is not limited to this method, and can be applied to formation of a capacitor insulating film of an MIM capacitor.
Reference numeral 45 denotes a gate electrode to be formed on the upper surface of the gate insulating film 4. For example, the gate electrode is made of a noble metal such as Pt (platinum) or a high melting point metal such as TiN or TaN, the noble metal and the high melting point metal not reacting with a polycrystal Si film, a polycrystal SiGe film or the gate insulating film 4. Reference numeral 46 denotes a channel region. P (phosphorous) or the like is injected into an n channel and B (boron) or the like is injected into a p channel, and those channels are heat treated at temperatures of 800 to 1,000° C. for 10 to 30 minutes to be activated. Reference numeral 27 denotes a first interlayer insulating film, which for example comprises SiO2 or the like and formed by CVD method or the like. Reference numeral 28 denotes an extraction electrode of the channel 46. The extraction electrode 28 is formed in such a manner that a contact hole is formed in the first interlayer insulating film 27 by means of RIE (reactive ion etching) or the like, and a high melting point metal, such as Cu, Al, AlSi, Pt2Si, TiN or TaN, is then provided in the contact hole.
Reference numeral 29 denotes a second interlayer insulating film to be formed on the upper surface of the first interlayer insulating film 27. The second interlayer insulating film 29 for example comprises SiO2, and formed by CVD method or the like. Reference numeral 30 denotes an extraction electrode to be provided in the second interlayer insulating film 29 so as to be electrically connected with one of the extraction electrode 28 to be formed in the first interlayer insulating film 27, and is formed in the same manner as the formation of the extraction electrode 28.
Reference numeral 31 denotes a capacitor to be provided in the second interlayer insulating film 29 so as to be electrically connected with the other extraction electrode 28 to be formed in the first interlayer insulating film 27, and is constituted as described below. Namely, a contact hole is formed in the second interlayer insulating film 29, and a lower electrode 32, an upper electrode 33 and a capacitor insulating film 34 to be formed between the two electrodes 32 and 33 are formed in the contact hole, and constitute the capacitor 31. The lower electrode 32 comprises a noble metal such as Pt or a high melting point metal such as TiN or TaN. The upper electrode 33 comprises a noble metal such as Cu, Al or Pt or a high melting point metal such as TiN or TaN. Either the electrode 32 or 33 is constituted of a material that does not react with the capacitor insulating film 34. The capacitor insulating film 34 is then formed using a high-k film on the upper surface of the lower electrode 32. It is to be noted that patterning is performed for example by means of the photolithography technique.
In order to test the performance of the capacitor insulating film 34, for example, a SiO2 film having a thickness of 200 nm was formed on the Si substrate, and on the upper surface thereof, a Pt film having a thickness of about 100 nm was formed, to give a lower capacity electrode. Subsequently, samples A to C were formed on the upper surface of the lower capacity electrode made of the Pt film, by the method shown in
It is found from Table 3 above that the dielectric breakdown voltage of each of the samples A to C according to the method of the present invention is higher than that of the sample D according to the conventional method, and hence the samples A to C are films of good quality. This is because, as apparent from Table 1, each of the samples A to C is a dense film of good quality having a large film density and containing a very small amount of impurities as compared with the sample D. It is therefore found that the high-k film according to the method of the present invention also has highly excellent properties as the capacitor insulating film 34.
It is to be noted that, although the Si substrate was used as the substrate on which the high-k film was to be formed in the above-mentioned embodiments, the substrate is not limited thereto, and a GaAs compound semiconductor substrate or a SOI (Silicon On Insulator) substrate may be used as the substrate.
As thus described above, according to the present invention, it is possible to form a gate insulating film made of a high-k film containing few impurities, so as to reduce flat band shift and an interface fixed charge due to the impurities, resulting in production of a high-quality MIS transistor. It is also possible to form a capacitor insulating film made of a high-k film containing few impurities, so as to prevent a decrease in dielectric break down voltage due to the impurities, resulting in production of a high-quality MIM capacitor.
Number | Date | Country | Kind |
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2003-79279 | Mar 2003 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP04/03638 | 3/18/2004 | WO | 7/12/2006 |