JPS61189645A - Surface treatment method - Google Patents

Abstract

PURPOSE:To enable thin film formation or thin layer etching of high accuracy in succession for a long time, by preventing the decrease in permeability of a photo transmission window for irradiation with photo energy, by a method wherein the raw material gas is absorbed to a substrate surface in the first reaction chamber, and the substrate surface is irradiated with photo energy in the second reaction chamber. CONSTITUTION:In the case of forming a thin film over a substrate 4, first, in the state of installing the substrate 4 in the first reaction chamber 1, it is evacuated by opening a valve 9. Next, the raw material gas is guided from a raw material gas source 3 through a valve 8 into the reaction chamber 1, and the raw material gas is adsorbed to the surface of the substrate 4, then, a residual of said gas is exhausted by opening the valve 9. Thereafter, the substrate 4 is transferred to the second previous ly evacuated reaction chamber 2 with a carrier by opening a partition 12, and is kept in the state of 4' in the figure. An ultrathin film of mono-atomic, monolayer or several-atomic, several-layer level is formed on the substrate 4' by irradiating it with the light of a light source 5 through a lens 6 and a photo transmission window 7. In this case, since the raw material gas does not flow into the second reaction chamber, the contamination of the photo transmission window for photo energy irradia tion and the decrease in photo permeability are not caused.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a method for surface treatment of thin films, and in particular to the formation of ultra-thin films at the level of monoatomic/monolayer or several atomic/several molecular layers or dry etching of ultra-thin layers. The present invention relates to surface treatment methods such as the following.

[Background of the invention]

2. Description of the Related Art As semiconductors become smaller and more highly integrated, there is an increasing demand for lower temperatures in surface treatment processes such as ultra-thin film formation and ultra-thin layer etching. In order to achieve this, attention has been focused on the photo-CVD method for forming thin films, and for etching, methods that utilize photo-induced chemical reactions. Atomic layer epitaxial methods and molecular layer epitaxial methods are attracting attention as methods for forming ultra-thin films at the level of monoatomic/monolayer or several atomic/several molecular layers. For details, see Applied Physics, Volume 5, No. 6, page 516 (1, 9
84), Nikkei Electronics, September 10, 1984
The date is listed on page 120. In this method, a source gas for forming a thin 11;:j (for example, when growing a GaAs thin film, trimethylgallium Ga (CH
A gas of an organometallic compound containing gallium such as 3h and a gas containing arsenic such as arsine As83 are alternately introduced into the reaction chamber and deposited layer by layer on the surface of the substrate, and in this state the substrate is heated and irradiated with light. It is known that it is possible to grow a monomolecular layer or several molecules of crystal at a time by 1"?I. Therefore, although it has the disadvantage of slow crystal growth, it is possible to grow an excellent film with extremely few crystal defects. In addition, the main reason why a method using light-induced chemical reactions is expected to be used as a new etching technology is that it enables low-temperature processing, reduces damage to the substrate to be etched, and etches only the light-irradiated area. This is thought to improve the spatial selectivity of the reaction.For example, the Sem1conductor World
d, 1984.11.103 page in detail. In the above-mentioned known example, it is revealed that the substrate surface is etched by photoactivating the etching gas adsorbed on the substrate surface. Looking at this phenomenon from a different perspective, it is predicted that in a system without replenishment of etching gas, the etching reaction will stop when the adsorbed etching gas is consumed. Therefore, while controlling the amount of etching gas adsorbed onto the substrate to be etched and exhausting the etching gas remaining in the reaction chamber to the outside of the system, the adsorbed gas on the substrate surface is photoactivated to allow the etching reaction to proceed. This suggests that controlled thin layer etching at the level of a single atom/monolayer or a few atoms/a few molecules is possible.

However, in the thin film forming method and thin layer etching method described above, at the same time that a thin film is formed on the substrate surface or the etching reaction progresses, a similar photochemical reaction is induced inside the light transmission window provided in these reaction chambers. Therefore, as each reaction progresses, reaction products adhere to the light transmission window, resulting in a decrease in the light transmittance of the light transmission window and the drawback that the photochemical reaction is inhibited.

[Purpose of the invention]

The present invention provides a surface treatment that eliminates the possibility that the light transmitting window for light energy irradiation provided in the reaction chamber becomes dirty and the light transmittance decreases, and enables high-precision thin film formation or thin film etching over a long period of time. My goal is to find a method.

[Summary of the invention]

In order to achieve the above object, the surface treatment method according to the present invention includes a first reaction chamber and a second reaction chamber, and a step of adsorbing a source gas onto the substrate surface in the first reaction chamber, and By including the step of irradiating light energy onto the substrate surface, a decrease in the transmittance of the light transmission window to which the light energy is irradiated is prevented, and an ultra-thin film at the level of a single atom/mono-molecular layer or several atoms/several molecular layers is formed. This method involves forming a thin layer or etching an ultra-thin layer.

[Embodiments of the invention]

Next, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a block diagram of an apparatus showing a first embodiment of the surface treatment method according to the present invention, FIG. 2 is a block diagram of an apparatus showing a second embodiment of the present invention, and FIG. 3 is a block diagram of a device showing a third embodiment of the present invention. FIG. 4 is a configuration diagram of an apparatus showing a fourth embodiment of the present invention; FIG. 5 is a partial explanatory diagram showing a fifth embodiment of the present invention; FIG.
7 is a partial explanatory diagram showing a seventh embodiment of the present invention. FIG. 8 is a partial explanatory diagram showing an eighth embodiment of the present invention. FIG. 9 is a partial explanatory diagram showing a ninth embodiment of the present invention. In the first embodiment shown in FIG. 1, a second reaction chamber 2 is provided adjacent to the first reaction chamber 1, and raw material gas is supplied to the first reaction chamber 1 from a raw material gas source 3 via a valve 8. A board 4 is installed inside. The light emitted from the light source 5 enters the second reaction chamber 2 through the light transmission window 7 via the lens 6. The first reaction chamber I and the second reaction chamber 2 are separated by a partition wall 12 that can be opened and closed between them, and are connected to an exhaust device 11 via valves 9 and 10, respectively. In this embodiment, when forming a thin film on the substrate 4, the substrate 4 is placed in the first reaction chamber 1, and the valve 9 is opened to evacuate the first reaction chamber 1. Next, the raw material gas is supplied from the raw material gas source 3 to the first reaction chamber 1 through the valve 8.
After the raw material gas is adsorbed onto the surface of the substrate 4, the remaining raw material gas is exhausted by opening the valve 9. After that, the partition wall 12 is opened and the substrate 4 is moved to the second reaction chamber 2 which has been evacuated in advance by a transfer device (not shown).
The substrate 4' is held in the state 4' in the figure, and the light from the light source 5 is irradiated onto the substrate 4' through the lens 6 and the light transmission window 7. Forms ultra-thin films at the layer level. Gas generated during the process of forming the ultra-thin film is exhausted by an exhaust device 11 by opening the valve 10. How to obtain the desired film thickness using this example.

The substrate 4' may be returned to the first reaction chamber 1 again and the above process may be repeated.

Incidentally, if an etching gas is used as the source gas, an ultra-thin layer can be etched by the same process, and etching to a desired depth can be obtained by repeating this process. As the etching gas, a gas containing a halogen element, which is often used in dry etching of semiconductors, is suitable.

The second embodiment shown in FIG. 2 is an example in which there are multiple types of source gas sources for forming a thin film. FIG. 2 shows two types of source gas sources 13 and 14, for example GaAs
It is effective for forming binary thin films such as. Ga
To take the case of As crystal growth as an example, the raw material gas source 13 contains arsine (As H3), the raw material gas source 14 contains
Trimethylgallium [Ga(CH3)3] may be used for this purpose. When forming a thin film in the second embodiment, it is sufficient to follow the same process as in the first embodiment. After the first reaction chamber 1 containing the substrate 4 is evacuated, the valve 15 is opened and the first raw material gas is AsH2 leaks from the source 13 and the substrate 4
The residual gas is adsorbed onto the surface of the gas, and the residual gas is exhausted through the valve 9. Next, the valve 16 is opened to supply Ga (C
H3) 3 is leaked and adsorbed onto the substrate 4. After that, the residual gas in the first reaction chamber is exhausted through the valve 9, and the partition wall 1
2.Open the board 4. is moved to the position of the substrate 4' in the second reaction chamber 2, which has been evacuated in advance. Then, the light from the light source 5 passes through the lens 6 and is irradiated onto the substrate 4' from the light transmission window 7 to form an ultra-thin film of a single atom/monomolecular layer or several atomic/several molecular layers on the substrate 4'. do.

Gas generated during the film formation process is exhausted by an exhaust device 11 via a valve 10. In order to obtain a desired film thickness according to this embodiment, the substrate 4' is returned to the first reaction chamber 1 and the process L is repeated.

The above embodiment describes a method in which the first source gas is adsorbed onto the substrate 4, and then the second source gas is adsorbed after exhausting.
1st. The second raw material gases may be mixed in a desired ratio and then introduced into the first reaction chamber 1 to be adsorbed onto the substrate 4. In this case, the step of adsorbing the source gas onto the surface of the substrate 4 is shortened.

The above embodiment described the formation of a binary crystal thin film, but
In the case of forming a ternary crystal, it is achieved by introducing another raw material gas source and performing the same process as above. That is, as a raw material gas, for example, arsine (AsH3),
Limethylpotassium A (Ga(CH3)3':l and trimethylaluminum (N!(CH3)3) are used as raw material gases, and these raw material gases are sequentially deposited on the substrate 4 in the evacuated first reaction chamber l. Afterwards, when light energy is irradiated in the second reaction chamber 2, Ga k
e An ultra-thin film of As can be obtained.

In the third embodiment shown in FIG. 3, a mask I7 with a desired pattern is installed at a position facing the substrate 4' of the second reaction chamber 2, and light from a light source 5 is irradiated through the mask 17. However, it is effective for selectively forming a thin film with a desired pattern on the portions of the substrate 4' that are irradiated with light. The apparatus configuration of this embodiment is the same as that of the first embodiment except for the mask 17, and when forming a thin film with a desired pattern on a substrate, the first
Follow the process of the example. That is, the substrate 4 on which the raw material gas has been adsorbed in the first reaction chamber 1 is transported to the second reaction chamber 2,
It is placed facing the mask 17 on which the desired pattern is drawn,
The light passing through the light transmission window 7 of the second reaction chamber 2 is transferred to the mask 1.
It is sufficient to irradiate the substrate 4' through the light beam 7. In order to grow a thin film with a desired pattern to a desired thickness, the substrate 4' that has been irradiated with light in the second reaction chamber 2 is returned to the first reaction chamber l.
The process from adsorption of the raw material gas to light irradiation in the second reaction chamber 2 may be repeated, but in this case, the steps are performed so that the relative positional relationship between the mask 17 and the substrate 4' is always constant. It is necessary to perform accurate positioning.

Note that etching gas was used as the raw material gas.

The etching residue is adsorbed onto the substrate 4 in the first reaction chamber 1,
By irradiating the substrate with light that has passed through the mask 17 in the second reaction chamber 2, a desired pattern can be selectively etched.

In the fourth embodiment shown in FIG. 4, a finely focused laser beam 18 is irradiated onto the surface of a substrate 4' that has adsorbed the raw material gas transported from the first reaction chamber 1 to the second reaction chamber 2. It is used when selectively growing a thin film or selectively etching a thin layer in the area irradiated with the laser beam 18. The structure other than the laser beam 18 is the same as that of the first embodiment shown in FIG. 1, and the process of forming a thin film or etching a thin layer is also the same as that of the first embodiment. To draw a desired pattern according to this embodiment, it is preferable to scan the substrate stand (not shown) that supports the substrate 4' in the second reaction chamber 2 in a two-dimensional direction parallel to the upper surface of the substrate 4'. In the Examples, in order to grow a desired pattern film to a desired thickness or to etch a desired pattern to a desired depth, the process starts from adsorption of the raw material gas in the first reaction chamber 1 to adsorption in the second reaction chamber 2. It is necessary to repeat the process up to the irradiation of the laser beam 18, but at this time, the same place on the surface of the substrate 4' is repeatedly irradiated with the laser beam 18.
Since it is necessary to perform irradiation using a computer, it is effective to introduce a computer-based design method. In addition, when performing selective etching of a thin layer according to this embodiment, a gaseous etching gas containing, for example, a norogen element is used as the raw material gas.

In the fifth embodiment shown in FIG. 5, instead of scanning the substrate table in a two-dimensional direction horizontal to the surface of the substrate 4' to obtain a desired thin film image in the fourth embodiment, a fixed substrate 4' An example of the main parts of an apparatus that scans a photocoupler to obtain a desired thin film image is shown below. Although the photocoupler 21 is located outside the second reaction chamber in the above example of the main part, the present invention is not limited thereto. In the embodiment described above, the laser beam 19 is sent through an optical fiber cable 20 to a photocoupler 21 incorporating a microlens or the like, and the laser beam 19 emitted from the tip of the photocoupler 21 irradiates the substrate 4'. The photocoupler 21 supported by the fixture 22 is moved by the action of the control unit 23, and as a result, forms a thin film with a desired pattern on the surface of the substrate 4' that has adsorbed the source gas, or forms a thin film with a desired pattern. can be etched.

Note that when etching is performed, an etching gas is used as the source gas.

In the sixth embodiment shown in FIG. 6, two laser beams are made to interfere, and the interference fringes are used to form a fine striped pattern on the substrate surface, and a shape corresponding to the pattern is formed. This is a method of forming a thin film or etching a thin layer. (a) is a diagram showing the configuration of the main parts of this device, with parts other than the mechanism for irradiating optical energy using interference fringes of laser light in the second reaction chamber being omitted. (b) is a diagram showing a striped pattern.

In FIG. 6 (al), a laser beam 25 emitted from a laser light source 24 is split into two laser beams 27 and 28 by a half mirror 26. Of the split laser beams, only one laser beam passes through the half mirror 26. The laser beam 27 is reflected by mirrors 29 and 30.31, respectively, to become a laser beam 32, and the laser beam 28 reflected by the half mirror 26 is reflected by mirrors 33, 34, respectively, to become a laser beam 35, and these two laser beams 32 and 35 interfere with each other to form interference fringes 36 on the surface of the substrate 4'.The adsorbed raw material gas is activated in the bright part 37 of the interference fringes 36, and the thin film forming reaction progresses in this part. To form the interference fringes, the first reaction chamber is evacuated, the raw material gas is adsorbed onto the substrate, the residual gas is evacuated, and the substrate is transferred to the second reaction chamber, as in each of the above embodiments. Pre-processes such as

In addition, if an appropriate etching gas is used as the raw material gas, the adsorbed etching gas will be activated in the bright areas of the substrate where interference fringes are present, and the photo-induced etching reaction will proceed, resulting in fine stripes on the substrate. Etching can be performed.

The seventh embodiment shown in FIG. 7 uses a reduction projection exposure system to
This figure shows a partial configuration when a desired pattern is irradiated onto the substrate adsorbing the source gas in the second reaction chamber. The process until the substrate is transported into the second reaction chamber 2 is the same as in each of the above-mentioned rows. The light that enters and exits the reduction lens 39 forms a reduced pattern of the pattern drawn on the mask 38 and projects and irradiates the substrate 4' on which the source gas has been adsorbed. Therefore, a thin film corresponding to the pattern of the mask 38 can be formed on the surface of the substrate 4', and by using etching gas as the raw material gas, a thin film corresponding to the pattern of the mask 38 can be formed on the surface of the substrate 4'. Thin layers can be etched.

The eighth embodiment shown in FIG. 8 shows a method for efficiently transporting the substrate and increasing the processing speed of thin film formation or thin layer etching. 41 is formed in an annular shape, and includes a pre-chamber 42 for introducing a substrate into the first reaction chamber 40, and a post-chamber 43 for carrying out the substrate on which thin film formation or thin layer etching has been completed in the second reaction chamber 41.
are provided at the tip of the first reaction chamber 4° and at the end of the second reaction chamber 41.

When forming a thin film or etching a thin layer according to this embodiment, first the partition wall 44 between the pre-chamber 42 and the first reaction chamber 40 is opened, and the substrates placed in the pre-chamber 42 are sequentially transferred by a transfer device. It is introduced into the first reaction chamber 40. At this time, the substrate 45 installed in the pre-chamber 42 is first moved to the position of the substrate 46, and the substrate 46 is advanced to the position of the substrate 47. Each substrate on the annularly formed transport device is sequentially moved clockwise by the action of a transport mechanism (not shown). The conveyance of the substrate progresses, and when the substrate 46 installed in the pre-chamber 42 reaches the position of the end 48 of the first reaction chamber 40, the conveyance stops, and at the same time, the partition wall 44 and the first reaction chamber 40 are separated from each other. The partition walls 50 and 51 between the second reaction chamber 41 are closed. Next, the first
After maintaining the pressure in the reaction chamber 40 at a vacuum, the raw material gas is introduced into the first reaction chamber 40, and the raw material gas is adsorbed onto the surface of each substrate from the substrate 47 to the substrate 48. Thereafter, the raw material gas remaining in the first reaction chamber 40 is exhausted, and the partition walls 44, 50, 51 are opened again to begin transporting the substrate. At this point, it is desirable that the inside of the second reaction chamber 41 be evacuated in advance. Then, the substrate 48 located in the first reaction chamber 40 is moved to the end 52 of the second reaction chamber 41 at position 11'1.
When it reaches the partition wall 44°50.
5], followed by a step of introducing the raw material gas into the first reaction chamber 40 and adsorbing the raw material gas onto the surface of each substrate newly transported to the first reaction chamber 40, and a step of exhausting the residual gas after adsorption. and implement. Meanwhile, the second reaction chamber 41 is evacuated and irradiated with light energy to the surfaces of the substrates introduced into the second reaction chamber 41 to advance the thin film formation or thin layer etching reaction on each of the substrate surfaces. Etching gas is used as the raw material gas for thin layer etching. Form a thin film of the desired thickness on each substrate surface or erase the thin layer of the desired depth.
In the case of ticking, the step of transporting the substrate from the pre-chamber 42 to the first reaction chamber 40 is stopped, the partition walls 50 and 51 are opened with the partition wall 44 closed, and the annular transport device is moved to transfer the substrate to the first reaction chamber 40. The substrate 48 of the reaction chamber 40 is located at the position of the substrate 52 of the second reaction chamber 41, and the J, (plate 52 of the second reaction chamber 41)
is advanced until it reaches the position of the substrate 48 in the first reaction chamber 40. At this time, the direction of movement of the substrate transport device may be clockwise or counterclockwise.

When each substrate reaches the above position, the partition walls 50 and 51 are closed, the raw material gas is introduced into the first reaction chamber 40 and the raw material gas is adsorbed on the substrate surface in the first reaction chamber 40, and then inside the reaction chamber 40. Exhaust the remaining raw material gas. During this time, while the second reaction chamber 41 is being evacuated, light energy is irradiated onto the substrate surface within the second reaction chamber 41 to advance a thin film forming reaction or thin layer etching on the substrate surface. The above steps are repeated until the thickness of the thin film on the substrate or the depth of the thin layer reaches a desired value, while the pre-chamber 4
The partition wall 44 between the pretreatment chamber 2 and the first reaction chamber 40 is closed, and the supply of substrates from the pretreatment chamber 42 to the first reaction chamber 40 is stopped. When the above-mentioned repeated process is completed and a thin film of a desired thickness is formed on the substrate surface or a thin layer is etched to a desired depth, in addition to the partition walls 44, 50, 51, the second reaction chamber 41 and the rear chamber 43 are etched. The partition wall 53 between them is opened, and the transport mechanism for the entire process is started. At this time, all the substrates placed in the second reaction chamber 41 no longer return to the first reaction chamber 40, but move one after another to the rear chamber 43.

In other words, the substrate 52 located at the end of the second reaction chamber 41 advances to the position of the substrate 54 in the rear chamber 43 in the first step, and to the position of the substrate 55 in the next step, and the substrate 56 of the second reaction chamber 41 advances to the position of the substrate 55 in the next step. The process continues until the substrate 54 in the rear chamber 43 is reached. During this time, all the substrates in the first reaction chamber 40 are moved into the second reaction chamber 41, and the first reaction chamber 40 has a front chamber 4.
A new board placed within 2 has been introduced. Here, regarding the substrates 56 to 52 newly introduced from the first reaction chamber 40 to the second reaction chamber 41, assuming that the desired number of times of thin film formation is N times, the thin film has already been formed N-1 times. It is in the state of being done. Therefore, the substrate 5 in the second reaction chamber 41
As for the substrates 56 to 52, all thin film formation steps are completed by performing the final light energy irradiation step, so the process can proceed to the step of transporting the substrates 56 to 52 to the rear chamber 43. The same applies to etching.

By introducing the substrate transport mechanism described in this embodiment, while the process of irradiating the substrate with light energy in the second reaction chamber 41 is carried out, the raw material gas is transferred to another substrate in the first reaction chamber. Since the knee step for adsorbing can be carried out in parallel, it is possible to speed up the throughput of film formation or layer etching.

The ninth embodiment shown in FIG. 9, like the eighth embodiment, is an effective method for increasing the throughput of thin film formation or thin layer etching. In this embodiment, the first chamber 59 and the second chamber 60 are always evacuated by exhaust pipes 57 and 58, and raw material gas is always injected.

Light energy emitted from the light source 5 through the lens 6 is transmitted through the lens 6 into the first reaction chamber, which is formed by adjoining a third chamber 62 supplied from a tube 61 and a fourth chamber 63 which is constantly evacuated. The second beam is introduced through the window 7 and irradiates the substrate 4'.
A fifth chamber 64 serving as a reaction chamber is further adjacent to each other, and partition walls 65, 66, 67, and 68 that can be opened and closed are provided between each of the adjacent chambers, and the opening and closing of each of the partition walls 65, 66, 67, and 68 is controlled by timing. The device is typically equipped with equipment (not shown) for transporting substrates into each of these chambers and programming for operating them.

The substrates 4 kept in a sufficiently exhausted state in the five first chambers and the second chamber 60 are transferred to the third chamber 62, and when the process of adsorbing the raw material gas onto the substrates 4 is completed, the third chamber 62 and The partition wall 67 between the fourth chamber 63 and the fourth chamber 63 is opened, and the substrate 4' adsorbing the source gas is transferred to the fourth chamber 63. At the end of this transfer, the partition wall 67 is closed. During this time, the source gas in the third chamber 62 diffuses into the fourth chamber 63, but since the partition wall 68 between the fourth chamber 63 and the fifth chamber 64 is closed, the source gas has the light transmission window 7. It does not flow into the fifth chamber 64. When the partition wall 67 is closed, the raw material gas that has diffused and flowed into the fourth chamber 63 is quickly evacuated through the exhaust pipe 69 and left in the fourth chamber 63.
In this case, it becomes undetectable in the gas phase. On the other hand, a new substrate 4 is transferred from the second chamber 60 to the third chamber 62, and at that time the partition wall 66 is opened, but since the partition wall 65 between the first chamber 59 and the second chamber 60 is closed, The raw material gas flowing from the third chamber 62 does not flow into the first chamber 59. 2nd room 60
When the substrate transfer from the first chamber 59 to the third chamber 62 is completed, the partition wall 66 is closed, and since the second chamber 60 is constantly evacuated, the vacuum state is immediately restored, and the space between the first chamber 59 and the second chamber 60 is then closed. The partition wall opens and new substrates 4 are supplied from the five first chambers to the second chamber 60.

On the other hand, in the fifth chamber 64, which is the second reaction chamber, light energy is irradiated onto the substrate 4' to form a thin film.
Since the substrate 4' is transferred from the 4th chamber 63 to the 5th chamber 64 after no source gas remains in the gas phase of the 4th chamber 63, the partition wall 68 between the 4th chamber 63 and the 5th chamber Even if the chamber is opened, the raw material gas will not flow into the fifth chamber 64. By having the apparatus configuration as described above, it is possible to eliminate the steps of introducing and stopping the raw material gas in the process step, and it is possible to implement flow operations suitable for the actual process.

If this embodiment is further expanded to include an annular conveyance mechanism as shown in the eighth embodiment, it is possible to efficiently form a thin film of a desired thickness or etch a thin film of a desired depth. It is effective in improving productivity.

As shown in the above embodiments, in the surface treatment method for thin film formation and thin layer etching according to the present invention, only the substrate on which the raw material gas has been adsorbed is sent to the second reaction chamber, which is a light energy irradiation chamber separated by a partition wall. Since the source gas does not flow into the second reaction chamber, it does not contaminate the light transmission window for irradiating light energy and reduce the light transmittance.

In the first to seventh embodiments described above, one substrate is installed in each of the first reaction chamber and the second reaction chamber, but the number of substrates can be increased to improve throughput. . Further, the mask 17 shown in the third embodiment is made by depositing a metal film on a light-transmitting plate such as quartz.

Therefore, the raw material gas is adsorbed onto the surface of the substrate 4 in the first reaction chamber, and after exhausting the residual gas in the first reaction chamber 1, the substrate 4 is transferred to the second reaction chamber, and the substrate 4 is moved relative to the mask 17. An adjustment process is required to maintain accurate positional relationships. Therefore, during the cycloprocess used to form a thin film of a desired thickness or perform etching to a desired depth, each time the substrate 4' is transferred to the second reaction chamber 2,
This means that an adjustment process must be provided for the above positioning. Mask 17 is a way to solve this problem.
The plate forming the plate may be made of a light-impermeable material, and the portion through which light is desired to be transmitted may be penetrated by etching or the like. With such a mask, the relative positional relationship between the mask and the substrate only needs to be defined once when the substrate 4 is installed in the first reaction chamber 1, and the substrate 4 is
There is no need to provide a step of adjusting the positional relationship each time ' is transported to the second reaction chamber 2.

In the eighth embodiment, when the substrates transported to the second reaction chamber 41 are irradiated with light from the light source, all the substrates in the second reaction chamber 41 may be irradiated at once.

Alternatively, a light source may move above the second reaction chamber 41 and irradiate light sequentially from the substrate 56 in a clockwise direction or in the opposite direction.

It goes without saying that it is effective to incorporate substrate heating means commonly used in the formation of semiconductor thin films, and can be applied to all of the above embodiments.

Although the above-mentioned embodiments mainly show examples of forming semiconductor thin films, the present invention can also be applied to photopolymerization processes for organic ultra-thin films using various monomers as raw materials.

〔Effect of the invention〕

As described above, the surface treatment method according to the present invention includes a first reaction chamber and a second reaction chamber, a step of adsorbing a raw material gas onto the substrate surface in the first reaction chamber, and a step of adsorbing the raw material gas onto the substrate surface in the second reaction chamber. By having a step of irradiating light energy to the second
Since the light transmission window provided in the reaction chamber is prevented from being contaminated by the reaction of the raw material gas, and a decrease in transmittance can be prevented, it is possible to continue forming ultra-thin films or etching ultra-thin layers for a long period of time. surface treatment is possible.

[Brief explanation of the drawing]

FIG. 1 is a block diagram of an apparatus showing a first embodiment of the surface treatment method according to the present invention, FIG. 2 is a block diagram of an apparatus showing a second embodiment of the present invention, and FIG. 3 is a block diagram of a device showing a third embodiment of the present invention. FIG. 4 is a configuration diagram of an apparatus showing a fourth embodiment of the present invention; FIG. 5 is a partial explanatory diagram showing a fifth embodiment of the present invention; FIG.
7 is a partial explanatory diagram showing a seventh embodiment of the present invention. FIG. 8 is a partial explanatory diagram showing an eighth embodiment of the present invention. FIG. 9 is a partial explanatory diagram showing a ninth embodiment of the present invention. 1.40...First reaction chamber 2.41...Second reaction chamber 3.13.14...Source gas source 4, 4', 45,46.47.48.52,54.
55.56...Substrate 5...Light source 7...Light transmission window

Claims (11)

[Claims] (1) A first reaction chamber and a second reaction chamber are provided, and the first reaction chamber adsorbs the raw material gas onto the substrate surface, and the second reaction chamber irradiates the substrate surface with light energy. surface treatment method. (2) The step of adsorbing the raw material gas onto the substrate surface is the first step.
The step of irradiating the substrate surface with light energy, which is performed after the step of evacuating the reaction chamber, is the step of transporting the substrate to the second reaction chamber after the step of evacuating excess raw material gas from the first reaction chamber. The surface treatment method according to claim 1, characterized in that the surface treatment method is carried out through the following steps. (3) The process from the step of adsorbing the raw material gas to the substrate surface to the step of irradiating the substrate surface with light energy is one cycle, and the cyclo process is repeated to form a thin film of a desired thickness or perform thin layer etching. A surface treatment method according to claim 1 or 2, characterized in that: (4) The surface treatment method according to any one of claims 1 to 3, wherein the light energy is light energy that has passed through a desired pattern drawn on a mask. (5) The surface treatment method according to any one of claims 1 to 3, wherein the light energy is light energy produced by a reduction projection exposure system. (6) The surface treatment method according to any one of claims 1 to 4, wherein the light energy is light energy from a laser light source. (7) The irradiation with the light energy is performed by fixing the position of the laser beam and moving the substrate, according to any one of claims 1 to 3 or 6. Surface treatment method to be described. (8) Claims 1 to 3, wherein the light energy is light energy emitted from a photocoupler guided from a laser light source through an optical fiber;
Or the surface treatment method described in any of Item 6. (9) The above-mentioned light energy is light energy obtained by dividing a laser beam and forming interference fringes with each of the divided laser beams. The surface treatment method described in Section 6. (10) The first reaction chamber and the second reaction chamber are arranged in an annular manner, and a pre-chamber and a post-chamber are connected to the tip of the first reaction chamber and the end of the second reaction chamber, respectively. Claim 1 characterized in that a conveying device is provided along the
The surface treatment method described in Items 1 to 9. (11) Each of the above steps is performed in separate adjacent rooms, and the timing of opening and closing the partition between each room and the timing of transporting the substrate to a predetermined position in response to the opening and closing are controlled by a program. The surface treatment method according to any one of claims 2 to 10, characterized in that the step of supplying or stopping the source gas is omitted.