Patent Document

BACKGROUND 
       [0001]    1. Field of Invention 
         [0002]    The present invention relates to a method of atomic layer deposition and an apparatus thereof. More particularly, the present invention relates to a deposition method for improving the atomic layer deposition performance. 
         [0003]    2. Description of Related Art 
         [0004]    Atomic layer deposition (ALD) is a unique method for depositing thin films with high quality. Compared with other film deposition methods, the atomic layer deposition method has the following benefits, excellent step coverage performance, superb conformality, low impurity content and precise thickness control. 
         [0005]    ALD is can closely relate to chemical vapor deposition (CVD) technique. The difference between the ALD and the CVD technique is that in the ALD technique the substrate for deposition is alternately exposed to only one of several complementary chemical environments and controlled within an appropriate temperature range to accomplish the films deposition. In the interval between pulsing the gaseous precursors to the substrate, generally, an inert gas is introduced to the chamber to purge the excess reactant of each pulse step. 
         [0006]    The self-limiting film growth process of the ALD performs a selective chemisorption between gaseous precursor and substrate surface and forms a film with atomic-scale thickness control. One ALD cycle of aluminum oxide (Al 2 O 3 ) deposition is can be a typical example of ALD surface reaction. Firstly a substrate surface with surface sites (—OH group) is exposed to the gaseous metal precursor (Trimethylaluminum, TMA) to carry out a selective chemisorb of the TMA until the surface sites are saturated. The ligand exchange by-product, methane (CH 4 ), is can be released from the substrate at high temperature. 
         [0007]    The TMA precursor can not be adsorbed any more on the substrate surface when all the available surface sites (—OH group) are occupied, After that, an inert gas, argon (Ar, for example), is introduced to purge the excess precursor gas which has not reacted with substrate surface and ligand exchange by-products. 
         [0008]    Next, pulsing an oxidant such as water (H 2 O) on the surface to react with methyl-group (CH 3 ) on the substrate surface and generate free —OH groups and gaseous methane. The adjacent —OH groups and the gaseous methane perform a dehydration reaction to bring out the methyl group. After purging the excess precursor and by-products form the surface, a desired aluminum oxide film with atomic scale is formed and it is ready for the next ALD cycle. This procedure ensures excellent conformality along with large area of uniformity as well as digital thickness control by selecting the number of deposition cycle repeated. 
         [0009]    Saturation behavior of an ALD reactant depends on many factors such as pulse/purge time, process pressure and process temperature, etc. the most important parameter to control the mechanism of an ALD process is the deposition temperature. Typically, a temperature region with a rather steady deposition rate, as known as ALD process window is observed, as shown in  FIG. 1 . 
         [0010]    In general, the process window of ALD is a compromise temperature range between all involved precursors. The process temperatures of different precursors; the process temperature of each precursor is a temperature range between the precursor condensation temperature and the precursor decomposition temperature. 
         [0011]    Some precursors that decompose in the high temperature region of a process window may harm the film quality and increase the impurity content of the film. 
         [0012]    For the foregoing reason, the conventional ALD process temperature should be chosen within the ALD process window. Taking the TMA/H 2 O process of ALD Al 2 O 3  as an example, the reactive surface sites of TMA precursor, —OH groups, are decreased in number with increasing temperature, leading to the decrease of Al 2 O 3  deposition rate. However, as higher deposition temperature can male the film more uniform and conformal, and contain lower impurity incorporation, which are mainly attributed to the faster H 2 O diffusion as well as the more complete surface reactions at higher temperature Similar situations can also occur on the case of TMA/ozone (O 3 ) process, O 3  decomposition at high temperature can critically relate to the deposition rate, uniformity and step coverage performance of an ALD process. 
         [0013]    Exactly as said, the process temperature is the most important factor in an ALD. The suitable process temperature range is specific for different precursors As above description, the conventional process window of the ALD is a compromise temperature range for different precursors so it is not easy to give consideration to ALD film properties and deposition rate in the meantime. 
       SUMMARY 
       [0014]    The present invention is directed to an atomic layer deposition method and the apparatus thereof, which satisfies the need of exactly temperature control in each ALD step. 
         [0015]    In accordance with the embodiments of present invention, the atomic layer deposition apparatus includes a chamber and a heating and cooling device set in the chamber. 
         [0016]    A wafer stage including a heater and a blowing duct is set in the chamber. The blowing duct can blow gas to diffuse heat of the heater and regulates the temperature of the chamber. 
         [0017]    The heating and cooling device is mounted over the wafer stage opposite to the wafer. The heating and cooling device includes a plurality of heating units and a plurality of gas inlets. The gas inlets provide the reaction gas from outside of the chamber wherein each gas inlet is independent and separate from others. 
         [0018]    Each heating unit includes a heat source and a cooler. The heat source generates thermal energy to increase the temperature of a deposited substrate in the chamber. The cooler is set around the heat source and to cool down the temperature of the heat source. 
         [0019]    In conclusion, the atomic layer deposition method applies the atomic layer deposition apparatus to alternate the process temperature of the different ALD steps rapidly, whereby the atomic layer deposition performance can be improved by the precise control of the process temperature. 
         [0020]    The process temperature of each step is determined in accordance with the specific precursor and the substrate surface used. In the case that a higher process temperature is needed, the heating units of the apparatus increase the temperature and maintains the temperature of the deposited substrate until the step is complete. 
         [0021]    When a lower process window is needed for the next ALD step, the heating units are turned off, and the cooler rapidly cool down the temperature of the deposited substrate. In addition, the blowing duct blows a gas to the heater and the deposited substrate to cool the heater and the deposited substrate. 
         [0022]    Because the process temperature is specific for different precursors, the embodiments of the present invention applying the atomic layer deposition apparatus to alternate the process temperature of each precursor. The apparatus alternates rapidly the deposition temperature ALD step; thereby the process temperature can be controlled precisely and simply. 
         [0023]    It should be understood that both the foregoing general description and the following detailed description are by examples, and are intended to provide further explanation of the invention as claimed. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0024]    The accompanying drawings are included to provide a further understanding of the embodiment of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings, 
           [0025]      FIG. 1  is a scheme of the ALD process window in accordance with prior art; 
           [0026]      FIG. 2A  is a schematic view of the atomic layer deposition apparatus in accordance with an embodiment of the present invention; 
           [0027]      FIG. 2B  is a schematic bottom view of a heating and cooling device of the atomic layer deposition apparatus in  FIG. 2A ; 
           [0028]      FIG. 2C  is an enlarged schematic sectional view of a heating unit of the heating and cooling device in  FIG. 2B ; and 
           [0029]      FIG. 3  is a diagram of an ALD procedure in accordance with an embodiment of present invention. 
       
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0030]    Reference will now be made in detail to the present embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts. 
         [0031]    Refer to the  FIG. 2A .  FIG. 2A  is is a schematic view of the atomic layer deposition apparatus in accordance with an embodiment of the present invention. The ALD apparatus  100  includes a chamber  105  and a temperature regulatory system set in the chamber  105 . The temperature regulatory system includes a wafer stage  110  and a heating and cooling device  130 . 
         [0032]    The wafer stage  110  supports a wafer  120 . The wafer stage  110  includes a heater  112  and a blowing duct  114 . The blowing duct  114  imports a gas to diffuse the temperature of the heater  112  or to cool the heater  112  as indicated by the bottom arrow. The blowing duct  114  also assists in cooling the temperature of the heater  112  when necessary. According to the embodiment of the present invention, the gas imported from the blowing duct  114  is a gas with a high heat capacity, such as helium (He). 
         [0033]    The heating and cooling device  130  is mounted over the wafer  120 , and includes a plurality of heating units  132 , a plurality of first gas inlets  134  and a plurality of second gas inlets  135 . The heating units  132 , the first gas inlet  134  and the second gas inlet  135  are arrayed to form a heating surface of the heating and cooling device  130 . The gas inlets  134 , 135  pulse the reaction gas from outside of the chamber  105 . 
         [0034]    It should be noted that each first gas inlet  134  and the second gas inlet  135  is independent and separate from others. The upper arrow shown in  FIG. 2A  indicates the reaction gas pulsed direction. An exhauster  140  removes the excess reaction gas and heat. 
         [0035]    In accordance with the embodiments of present invention, the reaction gas comprises Al(CH 3 ) 3 , H 2 O, O 3 , O 2 , SiCl 4 , ZrCl 4 , TiCl 4 , TaCl 5 , Hfl 4 , HfCl 4 , WF 6 , SiH 6 , NH3Hf(NEtMe) 4 , Zr(NEtMe) 4 , zirconium tetra-tert-butoxide, hafnium tetra-tert-butoxide, cyclopentadienyl strontium, cyclopentadienyl barium, and titanium isopropoxide. Refer to  FIG. 2B  and  FIG. 2C .  FIG. 2B  is a schematic bottom view of a heating and cooling device of the atomic layer deposition apparatus in  FIG. 2A .  FIG. 2C  is an enlarged schematic sectional view of a heating unit of the heating and cooling device in  FIG. 2B . The heating units  132  are arrayed to form a heating surface of the heating and cooling device  130 . Each heating unit  132  includes a heat source  133  and a cooler  136 . 
         [0036]    The heat source  133  generates the thermal energy to increase temperature of a deposited substrate  120  in the chamber  105 . The cooler  136  cools down the temperature of the heat source  133  and comprises a passage and a working fluid. The passage surrounds the heat source  133  through which the working fluid passes to rapidly dissipate the heat of the. In one embodiment of present invention, the heat source  133  is a coil to generate the thermal energy. A protecting lens  138  covered with the heat source  133 , and the protecting lens  138  is a sapphire lens or a ruby lens. 
         [0037]    It should be noted that the shape, number or arrangement of each component of atomic layer deposition apparatus shown in  FIG. 2A  to  FIG. 2C  are as exemplification, other shapes, numbers or arrangements are possible. For example, the arrangement, number and shape of the heating units  132 , the first gas inlets  134  and the second gas inlets  135  are not limited to the detail described in  FIG. 2A  to  FIG. 2C , any appropriate disposition is available. 
         [0038]    The atomic deposition method applies the ALD apparatus  100  to alternate the deposition temperature of the precursor pulse step and purge step rapidly, thereby the atomic layer deposition performance is improved. Because the process temperature is specific for different precursors and the ALD film quality is decided on the self-limiting film growth of the precursors, so the process temperature of each ALD step is decided in accordance with the film property demanded and specific precursor used. 
         [0039]    According to the embodiments of the present invention, the heating units  132  of the ALD apparatus  100  increase the temperature of the chamber  105  when the higher temperature is needed. At the same time, the heater  112  of the wafer stage  110  heats the deposited substrate  120  and the blowing duct  114  blows a gas to regulate the temperature of the heater  112 . 
         [0040]    If a lower process temperature is needed for the next step, the heating units  132  are turned off; the blowing duct  114  puffs a gas to the heater  112  and the deposited substrate  120  to cool down the temperature of the deposited substrate  120 . Further, the coolers  136  dissipate the heat of the heating units  132 . 
         [0041]    The TMA/H 2 O pulse step of the Al 2 O 3  deposition process is exemplified to explain the operational feature of the ALD apparatus  100 . The ALD apparatus  100  is capable rapidly changing the process temperature for the pulse step and purge step of ALD process. The TMA pulse temperature is controlled within the lower range of the process window to prevent the desorption behavior of the surface reaction, and consequently improve the film properties. On the other hand, the H 2 O pulse temperature is controlled within the higher range of the process window to accelerate the diffusion and decomposition of the H 2 O. 
         [0042]    Refer to the  FIG. 3 .  FIG. 3  shows the ALD procedure in accordance with an embodiment of the present invention. One cycle of the atomic layer deposition includes a first precursor pulse step (TMA pulse), a first precursor purge step (TMA purge), a second precursor pulse step (H 2 O pulse) and a second precursor purge step (H 2 O pulse). The ALD film thickness is controllable by selecting the number of deposition cycles repeated. 
         [0043]    In the beginning of the cycle, the first precursor pulse step is performed. At least one deposited substrate  120  is provided in the chamber  105 , and a first precursor is pulsed to the chamber  105  through the first gas inlets  134 . The heating units  132  are turned off and the temperature of the deposited substrate  120  is predetermined at the lower range within a process window. 
         [0044]    In this case, the lower limit of the process window is the precursor condensation temperature, and the higher limit of the process window is the precursor decomposition temperature. The term “higher range within a process window” designates a temperature range is approximately equal or beyond to the precursor decomposition temperature, and the term “lower range within a process window” designates a temperature range is lower relative to the precursor decomposition temperature. 
         [0045]    The predetermined temperature is an optimal temperature range for performing a selective chemisorb between the first precursor and the reactive surface sites of the substrate. 
         [0046]    The heater  112  of the wafer stage  110  is set at the lower temperature range within the ALD process window, and the blowing duct  114  puffs a gas to uniform the heat distribution over the deposited substrate  120 . The first precursor TMA has high deposition rates at the lower temperature range within the ALD process window, wherein the reaction formula for the TMA selectively chemisorbed is: 
         [0000]      Al—(OH) (solid) +Al(CH 3 ) 3(gas) →Al—O—Al(CH 3 ) 2(solid) +CH 4(gas) . 
         [0000]    Then, the first precursor purge step is performed. An inert gas is introduced into the chamber  105  through the first gas inlets  134  to purge the excess first precursor and by-products from the chamber. The heating units  132  are turned on to progressively increase the temperature of the chamber  105 , and reach the temperature at a higher range within or out the process window after the purging of the chamber is complete. The predetermined temperature of the heater  112  is slightly lower than the process temperature for cooling the heater  132  promptly. The blowing duct  114  puffs an inert gas to cool down the temperature of the heater  112  wherein the inert gas is selected from the group consisting of Ar, He, and N 2 . In embodiments of the present invention, an inert gas with higher heat capacity, such as helium (He), is suggested. 
         [0047]    Next, the second precursor pulse step is performed. A second precursor (H 2 O) is pulsed to the chamber  105  through the second gas inlets  135 . The heating units  132  are turned on and the temperature of the deposited substrate  120  is kept at the higher range within the process window by the heater  112  to selectively chemisorb the second precursor. The predetermined temperature of the heater  112  is slightly lower than the process temperature for cooling the heater  132  promptly. The blowing duct  114  puffs an inert gas, such as helium, to cool down the temperature of the heater  112 . The higher H 2 O pulse temperature is able to accelerate the H 2 O diffusion and complete the surface reactions of H 2 O selectively chemisorbed, wherein the reaction formula for the H 2 O selectively chemisorbed is: 
         [0000]      Al(CH 3 ) 3(gas) +H 2 O (gas) →Al—OH (solid) +CH 4(gas) . 
         [0048]    Finally, a second precursor purge step is performed. The step of purging the second precursor is carried out when the available surface sites (—CH 3  group) are saturated. All of the reaction gases, such as the precursors and ligand exchange by-products, are removed from the chamber  105 . 
         [0049]    An inert gas is introduced into the chamber  105  through the second gas inlet  135  to clean the surface of the deposited substrate  120 . Turn off the heating units  132  and start the cooler  136  to cool down the temperature of the heater  112 , and the temperature of the chamber  105  is decreased progressively. The blowing duct  114  puffs an inert gas to cool down the temperature of the heater  112  wherein the inert gas is selected from the group consisting of Ar, He, and N 2 . In embodiments of the present invention, an inert gas with higher heat capacity, such as helium (He), is suggested. 
         [0050]    According to embodiments of the present invention, further repeating one or more the ALD cycles to grow an ALD film with desired thickness. The ALD apparatus alternates the deposition temperature of each pulse step rapidly and the purge step improves the atomic layer deposition performance. 
         [0051]    Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred embodiments contained herein. 
         [0052]    It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.

Technology Category: 8