This application is based on Japanese patent application No. 2008-048,061, the content of which is incorporated hereinto by reference.
1. Technical Field
The present invention relates to an atomic layer deposition apparatus.
2. Related Art
Under the circumstance of enhanced miniaturizations and increased integrations of DRAM in recent years, one of the critical problems is to ensure larger cell capacitance. A technique for ensuring larger cell capacitance is an approach for adopting a high dielectric constant film (high-k film) for a capacitive film. Typical high dielectric constant films contain, for example, tantalum pentoxide (Ta2O5), hafnium dioxide (HfO2), zirconium dioxide (ZrO2) and the like. Typical processes for depositing such types of films include a sputter process, a metal organic chemical vapor deposition (MO-CVD) process, an atomic layer deposition (ALD) process and the like. The atomic layer deposition process is a process that involves proceeding depositions by every single atomic layer, and the process is advantageous as the deposition process can he carried out at a low temperature and in addition an enhanced quality of film can be easily obtained.
Japanese Patent Laid-Open No. 2004-288,900 discloses an ALD apparatus having two nozzles disposed to face across a substrate to be processed. These nozzles include hollow pipe members having a plurality of openings formed along the elongating direction, and are configured to discharge a process gas from the openings. In the apparatus disclosed in Japanese Patent Laid-Open No. 2004-288,900, the openings provided in the hollow pipe member are evenly distributed.
Japanese Patent Laid-Open No. 2002-151,489 discloses a substrate processing unit having a processing chamber, which is provided with a first and a second process gas-supply ports so as to face across a substrate to be processed, and is also provided with a first and a second slit-like exhaust ports in directions substantially perpendicular to flows of the first and the second process gases around the first and the second process gas-supply ports so as to face across a substrate to be processed. The following procedures are described in Japanese Patent Laid-Open No. 2002-151,489. The first process gas is flowed from the first process gas supply port toward the first exhaust port along the surface of the substrate to be processed so that the first gas is adsorbed in the surface of the substrate to be processed. Then, the second process gas is flowed from the second process gas supply port toward the second exhaust port along the surface of the substrate to be processed so that the second gas is reacted with molecule of the adsorbed first gas to form one molecular layered high dielectric film
Japanese Patent Laid-Open No. 2002-151,489 discloses a configuration, in which decreased inter-opening distances of the nozzles for the gas supply ports are provided in the central section and increased inter-opening distances are provided in both ends thereof.
However, it was found according to the investigations of the present inventors that the cell capacitances of the formed capacitors are varied and thus locations of deteriorated cell capacitances are created in the wafer surface, when a process gas is supplied over a wafer serving as a substrate to be processed from the evenly arranged nozzles to form a capacitive film of a capacitor as described in Japanese Patent Laid-Open No. 2004-288,900.
In the atomic layer deposition process, a metal source gas is first supplied to deposit a metallic source material on the substrate, and then the deposited layer of the metal source material is activated with an active gas such as ozone and the like to create a capacitive films or the like.
Japanese Patent Laid-Open No. H10-147,874 (1998) discloses that a flow rate of a reactive gas may be equalized by arranging the gas-supply ports having the feeding tubes for the deposition gas of the same diameter at inter-tube distances that are gradually decreased as being further from the gas supply tube. Japanese Patent Laid-Open No. H6-349,761 (1994) discloses nozzle tubes provided with larger number of gas supply pores, which are distributed at gradually decreased inter-pore distances as being further from the side of a gas inlet port toward the another end.
It is also described in the Japanese Patent Laid-Open No. H6-349,761 that such configuration provides uniform processing over the wafer.
A metal source gas and an active gas are employed in an atomic layer deposition process, as described above. The present inventors have found that a deterioration of the cell capacitance in the process with the atomic layer deposition apparatus as shown in
According to one aspect of the present invention, there is provided an atomic layer deposition apparatus, including: a substrate pedestal on which a substrate to be processed is disposed; a first gas feeding tube, disposed in a side of the substrate pedestal to extend over the entire surface of the substrate to be processed disposed on the substrate pedestal, and capable of being supplied with a source gas from one end to the other end; and a second gas feeding tube, disposed in a side of the substrate pedestal to extend over the entire surface of the substrate to be processed disposed on the substrate pedestal, and capable of being supplied with an active gas from one end to the other end, the active gas being active with a layer of a deposited material of the source gas over the substrate to be processed, wherein the second gas feeding tube is provided with a plurality of gas blow openings for blowing the active gas that is active with the substrate to be processed, and wherein the plurality of gas blow openings are distributed at inter-opening distances that are gradually reduced as being further from the one end toward the the other end of the second gas feeding tube.
Such configuration provides improved uniformity of the blowing rates of the active gas over the entire surface of the wafer, allowing improved uniformity in the processing with the active gas over the surface of the wafer. This inhibits partial deterioration of the cell capacitance as shown in
Here, any arbitrary combination of each of these constitutions or conversions between the categories of the invention such as a process, a device and the like may also be construed as being fallen within the scope of the present invention.
According to the the present invention, a partial deterioration over a wafer of the characteristics of a film deposited on the wafer through an atomic layer deposition can be prevented.
The above and other objects, advantages and features of the present invention will be more apparent from the following description of certain preferred embodiments taken in conjunction with the accompanying drawings, in which:
The invention will be now described herein with reference to illustrative embodiments. Those skilled in the art will recognize that many alternative embodiments can be accomplished using the teachings of the present invention and that the invention is not limited to the embodiments illustrated for explanatory purposed.
Exemplary implementations according to the present invention will be described in detail as follows in reference to the annexed figures. In all figures, an identical numeral is assigned to an element commonly appeared in the figures, and the detailed description thereof will not be repeated.
In the following embodiments, an atomic layer deposition apparatus supplies gases containing source materials over a substrate to deposit films via an atomic layer deposition process (ALD process), which involves depositing films by adsorbing by a unit of one atomic layer. The atomic layer deposition apparatus is capable of suitably conducting, for example; an operation for supplying a metal source gas over a substrate in a process chamber to adsorb a metal source material on the substrate, thereby forming a deposition layer; and an operation for supplying an active gas over the substrate in the process chamber to activate the deposited layer, formed by adsorbing the metal source material, with the active gas. Here, the adsorption may be a chemical absorption. Alternatively, the atomic layer deposition apparatus may be capable of depositing films via a plasma enhanced atomic layer deposition process by supplying at least a type of a plasma-excited gas over the substrate.
In the present embodiment, the atomic layer deposition apparatus 100 includes an external housing 102, a process chamber 106, a wafer pedestal (substrate pedestal) 104 on which a wafer 200 serving as a substrate to be processed, is disposed, a metal source gas supply tube 110 (first gas supply tube), an active gas supply tube 120 (second gas supply tube), an exhaust port 130, an exhaust port 140, and a quartz member 150. In
Here, a plurality of gas blow openings for blowing the gases are provided in the metal source gas supply tube 110 and the active gas supply tube 120, respectively. Gases are supplied to the metal source gas supply tube 110 and the active gas supply tube 120, respectively, from a lower end shown in
Next, the procedure for depositing films on the wafer 200 through the atomic layer deposition apparatus 100 in the present embodiment will be described in reference to
The depositions of the films on the wafer 200 are conducted in the atomic layer deposition apparatus 100 by repeating the following four process steps. In the first step, as shown in
In the third step, as shown in
In the present embodiment, the active gas may be selected from a group consisting of oxidized gas such as nitrogen monoxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O), oxygen gas (O2), ozone (O3) and the like, nitrided gas such as nitrogen gas (N2), ammonia (NH3) and the like, a gaseous mixture thereof, or a gaseous mixture thereof with argon (Ar) or helium (He).
Besides, the active gas may be a plasma-activated gas which is obtained by a plasma excitation of a gas selected from a group consisting of nitrogen gas (N2), ammonia (NH3) oxygen gas (O2), hydrogen gas (H2), a gaseous mixture thereof, or a gaseous mixture thereof with argon (Ar) or helium (He). When the plasma-activated gas is employed as an active gas, remote plasma, for example, may be utilized for the plasma excitation. Although it is not shown here, a remote plasma generation chamber including a gas inlet, a waveguide, and a microwave-applying unit, for example, may be provided in a location that is different from the location of the process chamber 106, and the plasma generated in the remote plasma generation chamber may be introduced to the active gas supply tube 120 via a tube such as a silica tube and the like.
In the present embodiment, the metal source gas may be, for example, a metallic material such as an inorganic metal compound such as metal halide and the like or an organometallic material and the like. The metal source gas may be selected from various types of materials employed in the ordinary ALD process. When the metal source gas is from solid or liquid material, the material is vaporized by employing a vaporizer or a bubbling device, which is not shown here, and then the vaporized material is supplied to the process chamber 106 with a carrier gas composed of an inert gas such as argon (Ar) and the like through the metal source gas supply tube 110.
For example, when a metallic compound film containing a metallic element of hafnium (Hf) or zirconium (Zr) is deposited, M(NRR′)4 may be employed as the metal source gas (where M contains at least one of Hf or Zr, and R and R′, which are different from each other, are hydrocarbon group). Here, alkyl group of 1C to 6C is preferable for R and R′, and more specifically, and typically methyl group, ethyl group, propyl group, tertiary butyl group and the like may be employed.
For example, when a metallic compound is employed for a capacitor element or a capacitive film of a decoupling capacitor, Zr(N(C2H5)2)4, Zr(N(CH3)2)4, Zr(N(CH3)(C2H5))4 and the like may be employed for the metal source gas. A selection of such compound provides a film having a smooth surface and a prevention of a contamination of the film with particles. As a result, a capacitive film having an improved film quality with smaller leakage current can be obtained. Besides, when a metallic compound film is employed for a gate insulating film of transistor for example, Hf(N(C2H5)2)4, Hf(N(CH3)2)4, Hf(N(CH3)(C2H5))4 and the like may be employed for the metal source gas. A selection of such compound provides more effective inhibition of a phenomenon of a penetration of impurity.
Next, the detailed arrangement of the gas blow openings will be described.
In active gas supply tube 120, an active gas is introduced from a first end 120a. A plurality of gas blow openings 122 are provided in the active gas supply tube 120. In the present embodiment, a plurality of gas blow openings 122 in the active gas supply tube 120 are aligned at gradually decreased inter-opening distances as being further from the first end 120a toward a second end 120b. This achieves an improved uniformity in the gas-blowing rates from the gas blow openings 122 in the upstream side and the downstream side.
On the other hand, the metal source gas is also introduced from a first end 110a in the metal source gas supply tube 110. The metal source gas may contain a carrier gas composed of an inert gas such as Ar and the like. A plurality of gas blow openings 112 are provided in the metal source gas supply tube 110. Here, the gas blow openings 112 of the metal source gas supply tube 110 may be evenly aligned from the first end 110a to a second end 110b.
While the gas blow openings 112 are evenly distributed in the metal source gas supply tube 110 in the example illustrated in
Alternatively, the atomic layer deposition apparatus 100 may be configured that the metal source gas supply tube 110 is provided in the same side as the active gas supply tube 120. Such configuration is shown in
Even in such case, the same arrangement as described in reference to
In such configuration, the first step involves supplying the metal source gas from the metal source gas supply tube 110 as shown in
The third step involves supplying the active gas from the active gas supply tube 120 and exhausting the gas from the exhaust port 130, which is located in the opposite side facing the active gas supply tube 120 across the wafer 200, as shown in
Next, advantageous effects obtainable by employing the configuration of the atomic layer deposition apparatus 100 in the present embodiment will be described. The present inventors have found that it is critical to provide uniform supply rate of the active gas over the wafer surface in the atomic layer deposition process, in which a metal source gas is first supplied to deposit a metal source material on a substrate, and then activating the deposited layer of the metal source material with an active gas such as ozone and the like to create a film. The metal source gas as described above is adsorbed by substantially one atomic layer irrespective of the time duration for supplying the gas, when the gas is supplied over the wafer 200. Therefore, despite the supply rate of the metal source gas is not uniform over the wafer surface, a uniform deposition is achieved over the wafer for a supply of a certain time duration provided that the supply rate is an ordinary level. On the other hand, a uniform supply of the active gas over the entire surface of the wafer is required, since it is considered that the process with the active gas cause a variation in the characteristics of the film according to the time for activation. The present inventors have found that the arrangement of the gas blow openings 122 in the active gas supply tube 120 is the most critical. In the present embodiment, the arrangement of the gas blow openings 122 may be configured to be optimum. This allows an optimization of the supply rate of the active gas so as to reduce a variation in the application of the active gas over the wafer surface, according to the atomic layer deposition apparatus 100 in the present embodiment. Therefore, uniform characteristics of the film in the wafer surface can be achieved.
On the other hand, it is not necessary to strictly determine the arrangement of the gas blow openings in the metal source gas supply tube 110 for supplying the metal source gas as in the case of the active gas supply tube 120. Therefore, uniform thickness distribution can be achieved over the surface of the wafer by employing the configuration of the evenly aligned gas blow openings 112 similarly as in the conventional configuration or employing a configuration similar to the optimized arrangement in the active gas supply tube 120. When the same tube as the active gas supply tube 120 is employed for the metal source gas supply tube 110, a spare gas supply tube may be commonly utilized for both tubes.
A configuration of preventing a rotation or the like of the wafer 200 within the process chamber 106 may often be employed in the atomic layer deposition apparatus 100 in order to reduce a generation of dusts. While such configuration causes a variation in the gas supply rate over the surface of the wafer, the arrangement of the gas blow openings 122 in the active gas supply tube 120 for supplying the active gas may be optimized according to the atomic layer deposition apparatus 100 in the present embodiment to provide uniform characteristics of the film over the surface of the wafer.
A transistor was formed on the silicon substrate, and a cylinder-like capacitor was formed above the transistor so as to be coupled to the diffusion layer of the transistor. The capacitor is formed to have, for example, a lower electrode composed of titanium nitride (TiN) and having a thickness of about 5 to 50 nm, a capacitive film having a thickness of about 5 to 15 nm, and an upper electrode composed of TiN and having a thickness of about 5 to 15 nm.
The capacitive film was manufactured in the following procedure. First of all, a metal source gas of Zr(N(CH3)(C2H5))4 was supplied in the process chamber of the atomic layer deposition apparatus with a carrier gas of Ar to cause a reaction in the surface of the lower electrode, growing only one atomic layer. Next, the supply of Zr(N(CH3)(C2H5))4 was stopped, and then an inert gas within the chamber was transferred therein as a purge gas to remove unreacted excessive Zr(N(CH3)(C2H5))4.
Subsequently, ozone (O3) was supplied as an active gas. Oxygen (O2) gas was introduced into, for example, a plasma generation chamber provided in a location separate from the location of the process chamber 106, which is not shown here, and exposing oxygen gas to a generated plasma to generate ozone, and then the generated ozone was introduced to the active gas supply tube 120 to cause a reaction with the one atomic layer formed on the lower electrode. Here, the introduced gas was substantially a gaseous mixture of ozone and oxygen. Next, the supply of ozone was stopped, and then an inert gas is introduced as a purge gas to remove unreacted reaction gas or byproducts, and then the supply of the purge gas was stopped. This serial cycles were repeated for only a desired cycles to obtain a capacitive film of zirconium oxide (ZrO2).
Here, the length of the metal source gas supply tube 110 of the atomic layer deposition apparatus 100 was equivalent to the length of active gas supply tube 120, and for example, the length was determined as a predetermined length selected from the range of from L=30 centimeters to 50 centimeters. In addition, number of the gas blow openings was determined as a predetermined number selected from a range of from 10 to 50 openings for each of the both gas tubes. In addition, the flow rate of the metal source gas containing the carrier gas of Ar was determined as a predetermined flow rate selected from a range of 0.1 to 2.0 standard liters per minute (slm) in both cases. The flow rate of the active gas was also determined as a predetermined flow rate selected from a range of 0.1 to 2.0 slm in both cases.
In such status, the following conditions were employed for the alignment of the gas blow openings in the metal source gas supply tube 110 and the active gas supply tube 120 to form the above-described capacitive film, and the distributions of the cell capacitance over the surface of the wafer were measured for the respective examples.
The arrangement of the gas blow openings 112 in the metal source gas supply tube 110: Evenly distributed.
The arrangement of the gas blow openings 122 in the active gas supply tube 120: the inter-opening distances were decreased as further from the inlet at a certain gradient, so that a=0.5 in formula (1) in
As shown in
The arrangement of the gas blow openings 112 in the metal source gas supply tube 110: the inter-opening distances were decreased as further from the inlet at a certain gradient, so that a=0.5 in formula (1) in
The arrangement of the gas blow openings 122 in the active gas supply tube 120: the inter-opening distances were decreased as further from the inlet at a certain gradient, so that a=0.5 in formula (1) in
Similarly as in the case shown in
The arrangement of the gas blow openings 112 in the metal source gas supply tube 110: Evenly distributed.
The arrangement of the gas blow openings 122 in the active gas supply tube 120: Evenly distributed.
As shown in
The arrangement of the gas blow openings 112 in the metal source gas supply tube 110: the inter-opening distances were decreased as further from the inlet at a certain gradient, so that a=0.5 in formula (1) in
The arrangement of the gas blow openings 122 in the active gas supply tube 120: Evenly distributed.
Similarly as in the case shown in
When the gas blow openings 122 are evenly aligned in the upstream side and the downstream side in active gas supply tube 120, the supply of the active gas is not sufficient in the downstream side of the active gas supply tube 120 when the the metallic layer deposited on the surface of the lower electrode is activated with the active gas. Therefore, it is considered that oxidation of the metallic layer cannot sufficiently proceed and thus organic compounds contained in the metal source material are remained in the film, as illustrated in EXAMPLE 3 and EXAMPLE 4.
On the other hand, when the gas blow openings 122 are distributed in the active gas supply tube 120 with the inter-opening distances that are gradually decreased at a certain gradient as being closer to the side of the downstream as illustrated EXAMPLE 1 and EXAMPLE 2, an improved uniformity in the total gas-blowing rates over the wafer surface can be achieved, and an improved uniformity in the oxidation of the metallic layer over the wafer surface can also be achieved. This allows reducing a partial deterioration of the cell capacitance as shown in
In addition, once the gas blow openings 122 are distributed in the active gas supply tube 120 with the inter-opening distances that are gradually decreased as closer to the side of the downstream as illustrated EXAMPLE 1 and EXAMPLE 2, uniform cell capacitance distribution over the entire surface can be obtained, regardless of employing the configuration of the even alignment of gas blow openings 112 in the metal source gas supply tube 110 or employing the configuration of the gas blow openings 122 in the active gas supply tube 120 with the decreased inter-opening distances. It is considered that this is caused because sufficient amount of the metal source gas is supplied over the entire surface of the wafer under the condition that the supply level of the metal source gas is within the illustrated range to achieve an adsorption of the source material by substantially single atomic layer. Therefore, the configuration of the even distribution of gas blow openings 112 in the metal source gas supply tube 110 or the configuration of the gas blow openings 122 in the active gas supply tube 120 with the decreased inter-opening distances may be employed.
As described above, the metal source gas is adsorbed by substantially one atomic layer irrespective of the time duration for supplying the gas, when the gas is supplied over the wafer 200. Thus, a uniform deposition is achieved over the wafer 200 when the time duration for supplying the metal source gas is set at a certain time duration provided that the supply rate is an ordinary level. However, the present inventor has found that under a certain condition, such as for example, when the time duration for supplying the metal source gas is set shorter than the ordinary level, the uniformity in the thickness of the capacitive film is lowered when the inter-opening distances of the gas blow openings 112 in the metal source gas supply tube 110 are decreased as further from the inlet at a certain gradient compared with the case when the inter-opening distances of the gas blow openings 112 in the metal source gas supply tube 110 are evenly distributed. Even with such the variation in the thickness of the capacitive film, as the quality of the capacitive film is improved by having the inter-opening distances of the gas blow openings 122 in the active gas supply tube 120 are decreased as further from the inlet at a certain gradient, the cell capacitances can be equally distributed over the entire surface. However, in order to achieve the strict uniformity over the entire surface for the cell, it is preferable to improve the uniformity in the thickness of the capacitive film as well.
Having such the situation into the consideration, the arrangement for the inter-opening distances of the gas blow openings 112 in the metal source gas supply tube 110 may be determined independently from the arrangement for the inter-opening distances of the gas blow openings 122 in the active gas supply tube 120. For example, as described in the above example 1, the arrangement of the gas blow openings 112 in the metal source gas supply tube 110 may be evenly distributed while the arrangement of the gas blow openings 122 in the active gas supply tube 120 is set as the inter-opening distances were decreased as further from the inlet at a certain gradient
While embodiments of the present invention has been fully described above in reference to the annexed figures, it is intended to present these embodiments for the purpose of illustrations of the present invention only, and various modifications other than that described above are also available.
While the exemplary implementations have been illustrated in the above-described embodiments, as described in reference to
It is apparent that the present invention is not limited to the above embodiment, and may be modified and changed without departing from the scope and spirit of the invention.
Number | Date | Country | Kind |
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2008-048061 | Feb 2008 | JP | national |