1. Field of the Invention
The present invention relates to a photo-assisted atomic layer deposition method, and more particularly, the present invention relates to a photo-assisted atomic layer deposition method capable of increasing reaction rate in the process of film depositions, reducing ligands in the deposited films and optimizing the atomic layer deposition.
2. Description of the Prior Art
Atomic layer deposition is a method to form a single atomic layer from the adsorbed molecule on the surface of the substrate. The atomic layer deposition is similar to the chemical vapor deposition (CVD), but every new atomic layer is relevant to the last atomic layer in the atomic layer deposition. Therefore, there is only one layer of molecules after every reaction. The atomic layer deposition is able to obtain a uniform thickness of layer deposited and an exact control of thickness by self-controlling and uniformly covering. Generally, two different kinds of gas reactants are introduced into the processing chamber in turn to deposit on the substrate in the atomic layer deposition. These gas reactants are called precursors.
Take Al2O3 deposition on a silicon substrate as an example. Firstly, the surface of the silicon which is predetermined to be deposited by Al2O3 is processed to absorb hydroxyls. Then, the precursor, Al(CH3)3, is introduced into the processing chamber. As Al(CH3)3 reacts with hydroxyls, a chemical bond is formed between aluminum and oxygen. CH4 is generated in the reaction and leaves the surface under the vacuum conditions. When the hydroxyl groups are completely reacted, Al(CH3)3 can no longer adsorb on the silicon surface, limiting the surface reaction to a single molecule scale. Then, residual Al(CH3)3 is removed, and water is introduced into the processing chamber. Water molecules react with methyl groups (CH3) to form the new hydroxyl groups atop of the alumina. The other two methyl groups react with water molecules to form oxygen bonds between two adjacent aluminum atoms through a dehydration reaction. A single atomic layer is formed after the processes mentioned above. The processes are repeated to form a plurality of atomic layers.
The atomic layer deposition is able to obtain a uniform thickness of layers deposited, an exact control of thickness, and a high aspect ratio. However, the deposition process is often limited by the choice of precursors which are required to possess high reactivity at a reaction temperature between 100 to 300° C. In addition, ligand residuals in the deposited films play a central role in the quality of deposited film. In the prior arts, plasma has been used to assist the complete decomposition of precursor involved in the reaction and to increase the deposition rate.
In the prior art, photo-assisted reaction is applied in a CVD system, wherein a transparent conduit is connected between a plasma generator and a CVD chamber, and an ultraviolet (UV) light illuminating the transparent conduit is provided to maintain the activation of the active species from the plasma generator. The disadvantages of the process in the prior art are as follows: (1) The temperature of the precursor illuminated by the UV light cannot be controlled independently, neither to the illumination time. (2) The long conduit is generally made of quartz or glass. A large portion of UV light is significantly adsorbed when the UV light passes through the long conduit, leading to a remarkable reduction of UV intensity and an ineffective illumination accordingly. (3) To provide the UV light with enough intensity, the power of the UV light should be enlarged, increasing the cost of facility. (4) Since the conduit is not spatially separated from the reaction chamber, there might be a plurality of films deposited on the inner wall of the long conduit, leading to the reduction of the transparence of the conduit quartz or glass.
As mentioned above, it is essential to provide a new photo-assisted atomic layer deposition method that are able to improve the reactivity of the precursor efficiently, to improve the growth rate, and to reduce the residuals of the ligand functional groups in the deposited films.
One scope of the present invention is providing a photo-assisted atomic layer deposition which comprises the following steps: preparing a processing system including a processing chamber and a plurality of gas input channels, wherein the processing chamber is used for containing a substrate and connected to a first gas input channel of the plurality of gas input channels, the first gas input channel includes a pre-chamber and a heating device, the pre-chamber includes a transparent side wall and is separated from the processing chamber by a first valve; starting the heating device to raise the temperature of the pre-chamber to a predetermined temperature; closing the first valve and introducing a first gas into the pre-chamber of the first gas input channel; illuminating the interior space of the pre-chamber by an ultraviolet light via the transparent side wall for a predetermined duration; and, opening the first valve to input the first gas illuminated by the ultraviolet light into the processing chamber to form atomic layers on the substrate.
Because the first gas is illuminated by the ultraviolet light in the pre-chamber of the first gas input channel, the reactivity of the first gas in the processing chamber is raised to form an atomic layer on the substrate efficiently. Besides, in the design of the pre-chamber, the planar transparent side wall is able to be made of the material with low absorption coefficient like MgF2, outperforming the prior art with the smaller illumination area and the less illumination intensity of the ultraviolet light.
The pre-chamber of the first gas input channel and the processing chamber are separable via a vacuum valve, so that the duration of illuminating the ultraviolet light is controllable separately. The temperature of the precursor illuminated by the ultraviolet light can also be controlled separately, so as to reduce the ligand residues of the precursor.
The pre-chamber of the first gas input channel and the processing chamber is separable via a vacuum valve to block any deposition occurred on the transparent side wall of the pre-chamber, so as not to degrade the illumination intensity of the ultraviolet light in the atomic layer deposition and the CVD process.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following step of: heating the pre-chamber to keep the temperature of the pre-chamber in a temperature range from 25° C. to 400° C.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the thickness of the atomic layer in every single deposition process is less than 1 nm.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, in the deposition process of atomic layer in the embodiment mentioned above, the predetermined duration of ultraviolet light illumination is in a range from 0.1s to 10s.
Another scope of the present invention is providing photo-assisted atomic layer deposition method; according to another embodiment, the wavelength of the ultraviolet light in the embodiment mentioned above is in a range from 160 nm to 360 nm, and the power is in a range from 100 Watts to 500 Watts. The temperature of the substrate heated by the processing chamber is in a range from 25° C. to 800° C. The flow rate of the react gas is in a range from 20 sccm to 5000 sccm.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the reacting gas in the embodiment mentioned above comprises at least one of Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Re, Fe, Co, Ni, Si, Ge, In, Sn and Ga compounds. The second gas comprises at least one of oxygen, water, hydrogen and nitrogen.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the transparent side wall of the pre-chamber in the embodiment mentioned above is made of one of magnesium fluoride, quartz and glass with high penetrability of the ultraviolet light.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following steps of: closing the first valve between the first gas input channel and the processing chamber to keep the first gas in the pre-chamber when the first gas is introduced into the pre-chamber.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following steps of: opening the first valve to input the first gas illuminated by the ultraviolet light into the processing chamber when the first gas has been illuminated by the ultraviolet light for a predetermined duration in the pre-chamber.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following steps of: introducing the second gas into the pre-chamber of the first gas input channel via a second gas input channel.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following steps of: introducing the second gas and the first gas from the pre-chamber into the processing chamber to form the atomic layer on the substrate.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following steps of: introducing the second gas into the processing chamber via the second gas input channel to form the atomic layer on the substrate.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises following steps of: introducing the third gas into the processing chamber via a third gas input channel.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the third gas introduced into the processing chamber via the third gas input channel is plasma gas or an inert gas, wherein the inert gas comprises nitrogen and argon.
Another scope of the present invention is providing a photo-assisted atomic layer deposition method; according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following steps of: alternatively opening and closing the first valve and a second valve which connects the second gas input channel to the processing chamber in turns, so as to introduce the first gas and the second gas into the processing chamber in turns to form the atomic layers on the substrate.
The advantages and spirits of the invention may be understood by the following recitations together with the appended drawings.
Some of the embodiments will be described in detail, with reference to the following figures, wherein like designations denote like members, wherein:
Please refer to
As shown in
In the step S10, the structures of the processing chamber 20 and the first gas input channel 22 of the processing system 2 were mentioned on the above paragraph. In practice, the processing chamber 20 and the first gas input channel 22 are able to be connected to different objects to achieve the process of the photo-assisted atomic layer deposition method. For example, the processing chamber 20 is able to be connected to an exhausting apparatus and another heating device to make suitable process conditions in the processing chamber. In another example, the first gas input channel 22 is able to be connected to a storage tank of the first gas G1. In practice, the processing chamber 20 is connected to another heating device to heat the substrate S in the processing chamber 20 to make the temperature in a range from 25° C. to 800° C. for the atomic layer deposition.
In step S12, the first gas G1 is introduced into the pre-chamber 220 of the first gas input channel 22. As mentioned above, the first gas input channel 22 is able to be connected to the storage tank of the first gas G1, so the first gas G1 is able to be introduced into the pre-chamber 220 from the storage tank. In step S14, the ultraviolet light is provided from an ultraviolet light generator. Please refer to
In the embodiment, because of the design of the pre-chamber 220 and the transparent side wall 2200, the first gas G1 can be effectively illuminated by sufficient ultraviolet light in the pre-chamber 220 to reduce the reaction time for each cycle. To make sure enough illumination on the first gas G1 by the ultraviolet light, the first gas G1 is able to stay in the pre-chamber 220 for a longer duration before getting into the processing chamber 20.
Please refer to
In step S12′, the first valve is closed when the first gas G1 is introduced into the pre-chamber 220 to keep the first gas G1 in the pre-chamber 220, so that the molecules of the first gas G1 can be illuminated by enough ultraviolet light in the follow-on steps. In step S16′, when the first gas G1 has been illuminated by the ultraviolet light provided by the step S14 for a predetermined duration, the first valve 222 is opened to introduce the first gas G1 into the processing chamber 20. The predetermined duration is determined by the parameters of the process and the system setup such as the kinds of the first gas G1 (precursor), the size of the processing chamber 20, and the kinds and the size of the substrate S. The first gas can be illuminated by enough ultraviolet light in the pre-chamber 220 by controlling the first valve 222.
In the atomic layer deposition, there are two kinds of process gases (precursors) which are introduced into the processing chamber in turns to form the atomic layers on the substrate; for example, trimethylaluminum and water are introduced into the processing chamber to form aluminium oxides on the substrate. Please refer to
In the step S12″ in the embodiment, when the first gas G1 is introduced into the pre-chamber 220, the first valve 222 is closed to keep the first gas G1 in the pre-chamber 220, and the second valve 240 is opened to input the second gas G2 into the processing chamber 20. Therefore, in the step S14, the first gas G1 is blocked in the pre-chamber 220 to be illuminated by the ultraviolet light. In the step S16″, as the first gas G1 is illuminated by the ultraviolet light for the predetermined duration, the first valve is opened to introduced the first gas G1 into the processing chamber, and the second valve 240 is closed to block the second gas G2 from entering the processing chamber 20. One atomic layer is formed after one cycle of the steps S12″ to S16″, and it moves forward to the step S12″ of the next cycle to form another atomic layer, as shown in
In practice, the first gas input channel 22 of the processing system 2 shown in
In addition to the first gas G1 and the second gas G2, the photo-assisted atomic layer deposition method of the present invention is able to utilize a third gas to assist the process. Please refer to
As shown in
Please refer to
The processing chamber of the photo-assisted atomic layer deposition method of the present invention is able to maintain a process temperature to keep the process fluent. Besides, according to another embodiment, the photo-assisted atomic layer deposition method further comprises the following step of heating the pre-chamber 420 by the heating device 424 to make the temperature of the pre-chamber 420 in a temperature range from 25° C. to 400° C. Therefore, the first gas G1 achieves a higher reactivity to make the deposition rate faster and the required illuminating duration shorter.
Please refer to
As shown in
In the embodiments, the second gas G2 can work as a precursor and be introduced into the processing chamber 60 from the pre-chamber 620. When the second gas G2 is a precursor, the first gas G1 and the second gas G2 can be introduced into the pre-chamber 620 and the processing chamber 60 in turns to form the atomic layers one by one. Please refer to
In the embodiments of
The photo-assisted atomic layer deposition method of the present invention utilizes the design of the pre-chamber in the gas input channel to enhance the reactivity of precursor molecules through an effective illumination of ultraviolet light. Therefore, the present invention provides a photo-assisted atomic layer deposition method utilizing the design of a pre-chamber through which the temperature of precursor molecules and the illumination of ultraviolet light can be well controlled, improving the reactivity, deposition rate and reducing the residues of the ligand functional groups of the precursor.
With the examples and explanations mentioned above, the features and spirits of the invention are well described. More importantly, the present invention is not limited to the embodiment described herein. Those skilled in the art will readily observe that numerous modifications and alterations of the device may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.
Number | Date | Country | Kind |
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104125979 | Aug 2015 | TW | national |