Patent Application
20100124621
1. Field of the Invention
The present invention generally relates to a method of forming an insulation film by plasma enhanced atomic layer deposition (PEALD).
2. Description of the Related Art
ALD is a method of forming a film that offers a great coverage, but it presents a challenge in terms of throughput. On the other hand, CVD can achieve high film growth rates, but its coverage is not as good as what can be achieved with ALD. Conventional PEALD is a method whereby the first key material is adsorbed to the surface of the target and then a reactant gas that has been activated by a plasma is supplied to cause surface reaction with the adsorbed material (refer to US2005/0037154 A1, for example). Since what is occurring is surface reaction, height gaps are covered effectively and a good coverage can be achieved. However, this reaction only involves the adsorbed material and thus the film growth rate is low. In particular, the first material is sometimes a polymer material, in which case there are unfavorable three-dimensional shapes that keep the adsorption amount low.
In some embodiments of the present invention, the film growth rate is increased while maintaining a good coverage, to achieve a high throughput. In other words, the material is broken down using a plasma into, say, a more active material having a smaller molecular weight and thereby increase the amount of material adsorbed to the surface, because then the film growth rate of ALD can be raised. In addition, the key operating principle of ALD is that material molecules are chemically adsorbed to the surface in a single layer until saturation. This is why a good coverage is achieved. Here, the intention is to partially activate the material, lowering the molecular size, and raise the adsorption amount. It should be noted, however, that the material may be adsorbed in multiple layers in some embodiments.
Under the method of forming a film proposed in some embodiments of the present invention, the precursor (also referred to as first material) is partially activated by use of a plasma, which means that the molecular weight of the material is lowered and the material is partially activated, and consequently more of this material thus activated is adsorbed to the surface. In the above, not all of the material is activated, and there are various species in terms of the activation degree, some of which are activated and some of which are not activated (the overall activation degree depends on plasma power), and in terms of the molecular size. If the activation degree of the material is high, the material may be adsorbed in multiple layers before the surface is sufficiently saturated, reducing the coverage property of deposition. In order to improve the coverage and the deposition rate, various species are generated wherein the material is partially decomposed and is partially activated by a plasma. Thereafter, a reactant gas that has been activated using a plasma is supplied to cause reaction with the first material now adsorbed to the surface to form and fix a film. In ALD, without the reaction with the reactant gas, the adsorbed material does not form a film. By the reaction with the reactant gas, a film is formed and fixed so that films can be stacked through multiple film-forming cycles to obtain a target film having a desired thickness. This sequence in a representative embodiment is shown in
As for applications, this method can be favorably applied to a gate spacer SiN film (at a film thickness of 25 nm, for example), among others, because it can achieve an insulation film offering good coverage.
For example, the PEALD (plasma enhanced atomic layer deposition) film growth rate of SiN film based on a prior art is 0.05 nm/cycle or less. If the thickness of the target SiN film to be used as a gate spacer is 25 nm, for example, 500 cycles are required (Tae-Ho Yoon et al., “low temperature plasma enhanced atomic layer deposition of silicon nitride,” abstract of ALD Conference 2008, Hodson C., “silicon nitride and silicon oxide thin film by plasma ALD,” abstract of ALD Conference 2008). More cycles means lower throughput. The sequence conforming to an embodiment of the present invention can achieve a film growth rate of approx. 0.15 nm/cycle based on a similar combination of material and reactant gas. This means that 167 cycles are needed to form a film of 25 nm in thickness, which is a significant improvement in throughput.
In a typical embodiment, a method of forming an insulation film by plasma enhanced atomic layer deposition (PEALD) comprises: (i) introducing a precursor into a reaction space where a substrate is placed; (ii) treating the precursor with a plasma; (iii) adsorbing the plasma-treated precursor onto a surface of the substrate (without forming and fixing a film); (iv) treating the adsorbed surface using a reactant gas and a plasma to form and fix a film, wherein steps (i) to (iv) constitute one cycle; and (v) repeating the one cycle multiple times until an atomic layer of a desired thickness (e.g., less than 100 nm, depending on the application; e.g., about 30 nm as a gate spacer) is obtained.
In some embodiments, no reactant gas is supplied in steps (i) to (iii). In some embodiment, the reactant gas is also supplied in steps (i) to (iii), wherein in order to control reactivity between the precursor and the reactant gas, a slow reaction compound such as non-metal, silicon-based compounds (as compared with metal-based compounds) is used as the precursor, and a less reactive gas such as nitrogen or nitrogen-containing gas (as compared with oxygen gas) is used as the reactant gas, thereby reducing generation of particles and efficiently removing unwanted deposition by cleaning. In the above embodiments, the slow reaction compound can be decomposed to smaller molecules and excited by a plasma, thereby enhancing adsorption of the smaller molecules onto a surface of the substrate. In some embodiments, a purge process is conducted between step (iii) and step (iv).
In some embodiment, RF power generating the plasma in step (ii) is lower than RF power generating the plasma in step (iv). For example, the RF power generating the plasma in step (ii) may be 1 to 100 W for a 300-mm substrate, and the RF power generating the plasma in step (iv) may be more than 100 W for a 300-mm substrate. In an embodiment, the RF power generating the plasma in step (ii) is less than about 1/10 of the RF power generating the plasma in step (iv). In an embodiment, the RF power generating the plasma in step (ii) is less than about 0.07 W/cm2 per area of the substrate (less than 50 W for a 300-mm substrate). If the RF power generating the plasma in step (ii) is high, multiple sub-layers may be adsorbed on the surface, thereby increasing the deposition rate, but diminishing step coverage.
In some embodiment, the plasmas in steps (ii) and (iv) are generated in a gap between capacitively-coupled parallel plate electrodes.
In this disclosure, “gas” may include vaporized solid and/or liquid and may be constituted by a mixture of gases. In this disclosure, the precursor, the reactant gas, and the rare gas may be different from each other or mutually exclusive in terms of gas types, i.e., there is no overlap of gases among these categories. Further, in this disclosure, any ranges indicated may include or exclude the endpoints.
For purposes of summarizing aspects of the invention and the advantages achieved over the related art, certain objects and advantages of the invention are described in this disclosure. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.
Further aspects, features and advantages of this invention will become apparent from the detailed description which follows.
These and other features of this invention will now be described with reference to the drawings of preferred embodiments which are intended to illustrate and not to limit the invention. The drawings are oversimplified for illustrative purposes and are not necessarily to scale.
a) shows a film formation cycle according to a conventional method.
b) shows a film formation cycle according to an embodiment of the present invention.
The present invention relates to PEALD; however, in conventional PEALD, applying a plasma to the precursor has never been considered. This is because the first step of ALD which is the process of adsorbing a material (Precursor) to a surface of the target is not a process of forming a film; but it is a process of substantially or nearly self-adsorption and self-saturation of the material (i.e., a non-film forming process) that adsorbs the precursor material onto a surface of a substrate. Thus, even when the amount of the precursor supply increases more than a certain amount, the amount adsorbed will not increase and adsorption will stop at the level where the surface is saturated. This saturation process leads to a good coverage; however, the film growth rate is very low because the activity of the precursor is low. In an embodiment of the present invention, by treating a precursor with a plasma in the process of adsorption to the surface, the molecular weight of the precursor is lowered and the decomposed precursor is excited, enabling an increase in the adsorbed amount. Materials for ALD tend to have high molecular weights, causing three-dimensional interference on a surface that keeps the adsorption amount low. Therefore, in some embodiments of the present invention, some molecules of the precursor are made smaller by applying a plasma (the adsorption species are formed in a gas phase), obtaining greater adsorption on the surface. As a result, the film growth rate is enabled to rise. However, if the molecules are highly activated, multi-layer adsorption occurs in some cases, increasing the film growth rate, but the coverage deteriorates. In some embodiments, the precursor is partially activated by a plasma so that some precursor species are non-activated or slightly activated, resulting in saturated adsorption and good coverage, and some precursor species are more activated, resulting in unsaturated adsorption, high deposition rate, and low coverage. By manipulating plasma power, the activation degree can be controlled, thereby obtaining a desired coverage and deposition rate. Precursor species which reach the substrate surface are adsorbed thereon. In PEALD, the material which has adsorbed on surface is reacted with a reactant, changing the adsorbed precursor material to a film-forming substance, and ultimately the deposition or formation of film.
In some embodiments, the precursor is excited by increasing the power of applied RF, which sometimes causes not single-layer but multilayer adsorption. The higher the RF power, the more the molecules are decomposed and activated. Active molecules sometimes cause multi-layer adsorption, increasing deposition rate but lowering the coverage. RF power is applied to the extent that some precursor species remain non-activated or slightly activated, achieving good coverage. Good coverage depends on the number of activated precursor species and their degrees of activation. To have good coverage (e.g., 80% or more), it is desirable to keep the power of applied RF low (e.g., for a substrate having a diameter of 300 mm, under 100 W, 80 W, 50 W, 30 W, and even under 10 W,) for adsorbing in the surface.
In some embodiments of the present invention, a silicon group material (or silicon-containing or silicon-based material) is used as a precursor. The silicon group material has a high gas phase pressure, is a stable material, and easy to use compared to a metal material which is used in the conventional PEALD. In addition, the silicon group insulation film is easy to clean and removable by cleaning before it peels (SiN, SiO, SiCN, etc. can be removed with NF3 radicals, O2 radicals, etc.). Moreover the reaction is moderate even when applying a plasma in the silicon group material. Therefore, silicon group material can be supplied simultaneously with a reactant (especially with reactant N2, N2O, etc., but not O2 etc., which has high reactivity), and even when a plasma is applied, the mixture does not causes the generation of particles or clogging of the showerhead.
The embodiments presented herein include those specified below. It should be noted, however, that the present invention is not at all limited to these embodiments:
1) A method of forming an insulation film by alternating multiple times, respectively, a process of adsorbing a precursor onto a substrate and a process of treating the adsorbed surface using a reactant gas and a plasma, wherein a plasma is applied in the process of supplying the precursor.
2) A method according to 1), wherein a reactant gas is not supplied in the precursor adsorption process.
3) A method according to 1) or 2), wherein a purge process is provided between the precursor adsorption process and plasma treatment process using a reactant gas.
4) A method according to any one of 1) to 3), wherein the precursor is at least one type of material selected from the group that includes silicon.
5) A method according to any one of 1) to 4), wherein the insulation film is constituted by a silicon compound.
6) A method according to any one of 1) to 5), wherein the reactant gas is NO2, O2, H2, CO2, N2O, N2 and/or NH3.
7) A method according to 5), wherein the silicon compound is SiO, SiN, SiC, SiON, SiCON, SiCO, SiBN, SiBO or SiCN.
8) A method according to 4), wherein the compound containing silicon is one of the aminosilane group.
9) A method according to any one of 1) to 8), wherein a reactant gas is also supplied in the precursor adsorption process.
10) A method according to 1), wherein the plasma power in the precursor adsorption process is lower than in the plasma treatment process using a reactant gas.
11) A method according to any one of 1) to 10), wherein the process pressures in the precursor adsorption process and plasma treatment process using a reactant gas are in a range of 50 to 2000 Pa.
12) A method according to any one of 1) to 11), wherein radio frequency waves are applied to the gap between the parallel plate electrodes to generate a plasma.
13) A method according to 12), wherein the high-frequency power applied in the precursor adsorption process is 1 to 500 W.
14) A method according to 13), wherein the high-frequency power applied in the precursor adsorption process is 1 to 100 W (in some embodiments it is under 80 W, 50 W, or 30 W).
In the embodiment of 2) above, reaction between the material and reactant gas in the gas phase can be suppressed because no reactant gas is supplied. Accordingly, a reactant gas is not supplied in the material supply process if the reactivity of material and reactant gas is high. This is because such high reactivity may result in generation of particles.
In the embodiment of 9) above, continuously supplying a reactant gas all the times improves throughput. No time for reactant purge is required, and thus, the cycle time can be shortened. In some cases, the embodiment of 9) improves the film growth rate. However, simultaneous supply of material and reactant gas followed by plasma application causes the material and reactant gas to react in the gas phase. To cause adsorption reaction to occur as close as possible onto the surface, therefore, reaction in the gas phase should be suppressed to an appropriate degree. If reaction progresses excessively in the gas phase, the film growth rate will rise but the coverage will drop. The coverage depends on the RF power as well as concentrations of material and reactant gas. If the reactivity of material and reactant gas is high, however, supplying the two simultaneously may result in particle generation.
The range of how much reactant gas should be supplied, ratio of reactant gas and material gas and other conditions in the embodiment of 9) above vary according to the types of material and reactant gas. When 3DMAS is used as the material, representative ranges of reactant gas flow rates are 0 to 900 sccm for N2; 0 to 500 sccm for H2; and 0 to 300 sccm for NH3 in an embodiment. If the material is 3DMAS-Cl, it reacts with H2 in the gas phase to generate particles. Among these, H2, for example, can be used effectively by supplying it in the reactant gas process, but not in the material supply process. As for N2 gas, in an embodiment it makes little difference whether or not N2 gas is supplied in the material supply process. In the case of NH3, too much supply of NH3 in the material supply process lowers the coverage in an embodiment. In an embodiment, the amount of material supply is estimated to be approx. 1 to 30 sccm.
In the embodiment of 1) above, representative examples of temperature range, range of processing time and flow rate range of precursor are shown below. The temperature range is 500° C. or below in an embodiment where the base method is PEALD involving application of plasma. In the case of thermal ALD where a plasma is not applied, on the other hand, high temperatures of 500° C. or above are required. The use of plasma makes the temperature range of the process to be low, such as 500° C. or below. In addition, a representative temperature range is 200 to 400° C. in the case of SiN film. With SiO film, a representative temperature range is from room temperature to 400° C. Lower temperatures provide an advantage from the viewpoint of application requirements. As for processing time, representative settings are 0.1 to 10 sec in the material supply process, 0 to 2 sec during purge and 0.5 to 10 sec in the reactant gas supply process. RF is applied in the material supply process. Typically when 3DMAS is used as the material, 100 to 500 sccm of carrier gas is used and the flow rate of 3DMAS is estimated to be 1 to 30 sccm. The same applies when HEAD is used.
The processing time mentioned above refers to the time during which precursor is supplied and radio frequency waves are applied.
In the embodiment of 1) above, representative examples of temperature range, range of processing time and flow rate range of precursor for plasma treatment using a reactant gas are shown below. In an embodiment, only one plasma processing temperature is required regardless of the type of precursor adsorption process, where this one temperature is normally 500° C. or below or preferably 200 to 400° C. The plasma treatment time using a reactant gas is typically 0.5 to 10 sec. The flow rate of reactant gas is approx. 100 to 1000 sccm for H2 and also 100 to 1000 sccm for N2, for example. The processing time mentioned above refers to the time during which a reactant gas is supplied and radio frequency waves are also applied.
In the embodiment of 3) above, representative examples of type of gas, flow rate range of gas, range of purge processing time and pressure are shown below. In the purge process, material is not supplied but inert gas, such as Ar, is supplied by approx. 100 to 3000 sccm. A reactant gas may be used in the purge process in some embodiments. Typically the purge time is 0 to 2 sec, while the pressure is typically 200 to 500 Pa, or approx. 50 to 2000 Pa in other embodiments. Note that typically evacuation is not performed after the purge. The purge time above refers to the time during which the atmosphere is exhausted while gas is still being supplied.
In the embodiment of 3) above, conversely a purge process may be provided in the same manner between the plasma treatment process using a reactant gas and the precursor adsorption process. However, this purge can be omitted in some cases. The chances of this purge being omitted without presenting problems are high, so long as all gases used in the plasma treatment process using a reactant gas and in the material adsorption process are the same, except for the material gas(es).
In the embodiment of 10) above, desirably the RF power should be 100 W or less in the material supply process and 100 W or more when a plasma is applied under reactant gas. The plasma power affects the film growth rate/coverage in the material supply process, while in the reactant gas supply process it is considered to affect the film quality primarily and film growth rate to some extent. Accordingly, the plasma power can be adjusted as deemed appropriate. In an embodiment, the RF power in the precursor adsorption process may be 5 to 50% (in some embodiments it may be under 20% or 10%) of the RF power used in the plasma treatment process.
In the embodiment of 13) above,
In relation to the embodiment of 13) above, the plasma power is typically 100 to 2000 W, or preferably 100 to 1000 W, in the plasma treatment process using a reactant gas.
In the embodiment of 12) above, typically the radio frequency range is around 13.56 MHz. In other embodiments, frequencies in a range of 400 kHz to 3 GHz may be used.
In an embodiment of the present invention, HEAD (Si2[NHC2H6]6), 3DMASCl (Si[N(CH3)2]3Cl), 3EMAS (H2Si[N(C2H5)CH3]3), 4DMAS (Si[N(C2H6)2]4), 4DEAS (Si[N(C2H6)2]4) and other materials belonging to the aminosilane group can be used as the first material (precursor). Other materials that can be used include SiH4, Si2H6, TSA ([SiH3]3N), HCDS (Si2Cl6), Si3H8, TICS (Si[NCO]4), TBOS (Si[OtBu]3OH), TDMHyS (Si[NHMe2]4), among others. Only one type of precursor may be used alone, or two or more types may be combined together.
In an embodiment of the present invention, the reactant gas may be N2, H2, O2, NH3, CH3, CO, C2H6, CO2, N2O, B2H6, etc., (only one type of reactant gas may be used alone, or two or more types may be combined together). Depending on the reactant gas(es) used, such films as SiN, SiO, SiON, SiCN, SiC, SiCO, SiCON, SiON, SiBN, SiBO, etc., can be formed.
(1) No purge process is provided after the reactant gas supply process.
(2) Reactant gas is supplied after the material gas supply process, after which RF is applied.
(3) (1) and (2) are combined.
(4) Supply of reactant gas is started after the purge process following the completion of material gas supply process, after which RF is applied.
(5) Reactant gas is supplied during the cycle process.
(6) Reactant gas is supplied during the cycle process, and no purge is performed after the application of high RF power.
(7) Reactant gas is supplied during the cycle process, and no purge process is provided.
(8) Reactant gas is supplied during the cycle process, no purge process is provided, and the RF power is constant.
(9) Supply of reactant gas is started in the middle of the material supply process.
(10) Supply of reactant gas is started in the middle of the material supply process, and no purge is performed before the material supply process.
(11) Supply of reactant gas is started in the middle of the material supply process, and no purge is performed.
(12) Application of RF power is always on and the power is changed successively.
(13) Reactant gas is supplied during the material supply process.
(14) RF is applied in the middle of the material supply process.
(15) RF is applied in the middle of the material supply process, and no purge process is provided.
(16) RF is applied only at the beginning of the material supply process, a purge process is provided, and RF is applied after the supply of reactant gas.
In the above, in one cycle in some embodiments, a duration of a precursor pulse overlapped by an RF pulse may be in a range of 0.2 to 5 seconds (preferably 0.2 to 2 seconds), a duration of a reactant pulse overlapped by an RF pulse without a precursor pulse may be in a range of 0.2 to 5 seconds (preferably 0.2 to 2 seconds), and an interval between the duration of the precursor pulse overlapped by the RF pulse and the duration of the reactant pulse overlapped by the RF pulse may be in an range of 0 to 5 seconds (preferably more than 0 but less than 2 seconds).
In the present disclosure where conditions and/or structures are not specified, the skilled artisan in the art can readily provide such conditions and/or structures, in view of the present disclosure, as a matter of routine experimentation. Also, in the present disclosure, the numerical numbers applied in specific embodiments can be modified by a range of at least ±50% in other embodiments, and the ranges applied in embodiments may include or exclude the endpoints.
In this example, the apparatus shown in the schematic diagram of
A Si wafer (300 mm in diameter) is heated to 400° C., and then HEAD Si2[NHC2H6]6 being the first material, N2 being the reactant gas, as well as Ar being the carrier gas and purge gas, are introduced, with the reactor pressure adjusted to approx. 400 Pa. The material carrier gas (any gas can be used as long as it is inert; Ar was used in this example, but the carrier gas may be the same as or different from the purge gas) was adjusted to a flow rate of 300 sccm (which resulted in a material gas flow rate of approx. 1 to 30 sccm), while the flow rate of reactant gas N2 was adjusted to 500 sccm. Ar purge gas was introduced (1 SLM) and the pressure was retained at a specified level for 1 min, after which material HEAD was supplied together with carrier gas (by precursor pulses) for 1 sec. Subsequently, the material supply was stopped and the purge process was provided (for 1 sec). Then, the reactant gas N2 was introduced (in the reactant step) for 1 sec, after which the supply of reactant gas was stopped and the purge process was implemented (for 0.5 sec). RF (13.56 MHz) was applied by 30 W in the material supply process and by 500 W in the reactant gas supply process. For comparison purposes, a similar operation was performed without applying RF in the aforementioned material supply process.
Also note that in sequence B in the present example, changing the RF power in the material supply process changes the film growth rate.
For example, assuming that a side coverage of 90% or more is desired for trenches with an aspect ratio (depth/opening width) of 3, if the RF power is 50 W or less, the required film can be formed at a growth rate of up to 0.1 nm/cycle. If the desired coverage is 85% or more, the required film can be formed at a growth rate of up to 0.15 nm/cycle with a RF power of 100 W or less.
As explained above, the method explained herein can increase the film growth rate and thereby improve the throughput to the extent that the coverage, which is a function of the RF power, is acceptable.
Furthermore, the film formed according to the present example was confirmed to have a minimum plasma damage and the uniformity of film thickness was also excellent at 1σ=1.0%.
It should be noted that an appropriate film forming pressure is 50 Pa to 2 kPa, partly because a plasma can be maintained at pressures in this range and partly because the coverage becomes higher as the pressure increases.
In accordance with Example 1, a SiO2 film was formed using BDEAS(bis(diethylamino)silane, SiH2[N(C2H5)2]2 as the first material and O2 (900 sccm, supplied for 1 sec) as the reactant gas. Therefore, when a conventional PEALD sequence (
Further, the film growth rate increased to 5 nm/cycle when RF was applied by 20 W in the first material process while O2, being the reactant gas, was being supplied (by 300 sccm). However, this led to generation of particles also at the shower head which is the gas introduction mechanism. This is probably because reaction occurring in the gas phase resulted in a CVD reaction.
In accordance with Example 1, a film was formed in the same manner as in Example 1, except that 3EMAS (tris(ethylmethylamino)silane, H2Si[N(C2H5)CH3]3 was used as the first material, 3EMAS was supplied simultaneously with the first reactant gas N2 (300 sccm), RF was applied by 30 W, and then RF was turned off and the atmosphere was purged, followed by supply of the second reactant gas H2 (500 sccm) and application of RF by 500 W. As a result, or specifically as a result of applying the reactant gases and RF in the first material supply process, the film growth rate increased (achieved film growth rate=0.1 nm/cycle).
In accordance with Example 1, 4DMAS (tetra(dimethylamino)silane, Si[N(C2H6)2]4 was used as the first material and N2O was used as the reactant gas. When 3DMAS and N2O were supplied simultaneously, RF was applied by 10 W, after which RF was turned off and the supply of 3DMAS was stopped, followed by a purge time and application of RF by 500 W, a SiON film was formed at a film growth rate of 0.3 nm/cycle.
It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention.
This application claims the benefit of U.S. Provisional Application No. 61/114,847, filed Nov. 14, 2008, and the disclosure of which is herein incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61114847 | Nov 2008 | US |
