JPH05106046A - Chemical vapor deposition apparatus and production of x-ray mask - Google Patents

Abstract

PURPOSE:To provide a CVD apparatus on an induction heating system capable of simultaneously depositing a grown film onto both sides of a substrate and also to provide an X-ray mask producing method where the process of the growth on both sides can be simplified by using the above apparatus and the deterioration in the film quality and adhesive strength of the both sided grown film can be prevented. CONSTITUTION:The apparatus is a CVD apparatus where an Si substrate 1 is arranged in a manner to be separated 3 from a susceptor 2 and also is arranged in the vicinity of the susceptor 2 in a manner to be in parallel with the susceptor 2 and a chemical vapor deposition film 4 is deposited simultaneously on both sides 1A, 1B of the substrate 1. Because a gap exists between the Si substrate 1 and the susceptor 2, a first SiC film to be a membrane is formed on the surface 1A of the substrate and a second SiC film to be an etching mask is formed on the rear surface 1B of the substrate. By this method, the X-ray mask manufacturing process can be simplified and, simultaneously, the improvement in the Si supporting frame forming precision and the prevention of the peeling of absorber pattern can be effectively done and yield can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high frequency induction heating type chemical vapor deposition (CVD) apparatus, and an X method using the same.
The present invention relates to a method for manufacturing a line mask.

FIG. 5 shows a method of manufacturing an X-ray mask.
As shown in (a), the first silicon carbide (SiC) of the membrane material is formed on the front surface and the back surface of the silicon substrate 51 by the CVD method.
The film 52 and the second SiC film 53 of the etching mask material are formed in separate steps, and then, as shown in FIG. 5 (b), the first SiC film 53 is formed.
An X-ray absorber film 54 such as tantalum (Ta) is formed on the film 52 by a sputtering method, and then a second SiC film is formed as shown in FIG. 5 (c).
An opening 55 for etching is formed in the film 53, and then, as shown in FIG.
As shown in FIG. 3, after the second SiC film 53 is placed on the ceramic support substrate 57 having the second light-transmitting window 56 with the second adhesive layer 58, the second SiC film 53 is placed on the ceramic support substrate 57. Back-etching 59 with a fluorinated nitric acid-based jet solution is performed on the silicon substrate 51 through the translucent window 56 and using the second SiC film 53 as a mask through the etching opening 55 to form the first SiC film on the silicon substrate 51.
By forming the first translucent window 60 exposing the back surface of 52, as shown in FIG. 5 (e), the first SiC film 52 is formed on the silicon support frame 51F made of the silicon substrate 51. , A SiC membrane with an X-ray absorber film 54 deposited on top
There is a step of forming a mask blank in which 52M is stretched and then patterning the X-ray absorber film 54 to form an X-ray absorber pattern (mask pattern) 54P as shown in FIG. 5 (f).

In the manufacturing process of such an X-ray mask, in order to reduce the number of processes and prevent the deterioration of the quality of the SiC membrane and the SiC films 52 and 53 for the etching mask,
A high frequency induction heating type CVD apparatus capable of simultaneously depositing a good quality SiC film on both surfaces of a silicon substrate has been desired.

[0004]

2. Description of the Related Art A conventional high-frequency induction heating type CVD apparatus used in the manufacturing process of the above X-ray mask is shown in FIG.
As shown in the schematic cross-sectional view of the main part of the carbon susceptor 103 arranged in the quartz reaction tube 101 via the quartz jig 102 and the like.
The silicon substrate 51, which is the substrate to be grown, was directly contacted and fixed on both surfaces of the silicon substrate 51 via the supporting mechanism 104, and the vapor phase growth of, for example, the SiC film was performed on the silicon substrate 51. .. In FIG. 5, 105 is a growth gas inlet, 106 is a vacuum exhaust port, and 107 is a high frequency coil.

[0005]

However, a CV having a conventional structure is used.
In the D device, the carbon susceptor 103 is formed on one surface of the growth substrate.
Since they are in contact with each other, the SiC film can be grown only on one surface of the substrate to be grown, for example, the silicon substrate 51 in one growth, so that the SiC film is grown on both surfaces of the silicon substrate 51 as in the X-ray mask manufacturing process described above. In the case of growing the films 52 and 53 respectively, there is a problem that the growth process needs to be performed twice by reversing the substrate, which complicates the manufacturing process.

Further, even if the back surface side of the silicon substrate 51 which is the substrate to be grown is in contact with the susceptor 103, it is not in a completely adhered state. When the SiC film 52 of No. 1 is grown, the SiC film also wraps around on the back surface side and grows thin. And this wraparound growth film becomes a poor quality SiC film with poor adhesion due to insufficient supply of the reaction gas. Therefore, in the second growth step, the second SiC for the etching mask is formed on the back surface of the silicon substrate 51. There is a problem that when the film 53 is grown, its film quality and adhesion are deteriorated, and its masking property is deteriorated. Also, in the second growth step, similarly, the film is formed on the first SiC film 52 for the membrane. There is a problem in that the second SiC film having poor adhesiveness wraps around and causes peeling of the absorber pattern 54P deposited on the membrane 52M.

Therefore, the present invention provides a high-frequency induction heating type CVD apparatus capable of simultaneously depositing a good quality growth film on both surfaces of a substrate to be grown, thereby simplifying the double-sided growth process and simultaneously The purpose is to prevent deterioration of the quality and adhesion of the growth film.

[0008]

FIG. 1 is an explanatory view of the principle of the present invention, in which 1 is a growth substrate, 1A is the surface of the growth substrate,
1B is the back surface of the substrate to be grown, 2 is a susceptor, 3 is a gap (gap), and 4 is a chemical vapor deposition film.

As shown in FIG. 1, the solution to the above problem is a high frequency induction heating type CVD apparatus in which a growth substrate (1) is separated (3) from a susceptor (2) to be induction heated. A chemical vapor deposition method according to the present invention, which is arranged in the vicinity of the susceptor substantially parallel to the susceptor (2) and simultaneously deposits a chemical vapor deposition film (4) on both surfaces (1A) (1B) of the substrate (1) to be grown. When forming a first silicon carbide film that serves as a membrane on the surface of a vapor phase growth apparatus or a silicon substrate that serves as a support frame, and forming a second silicon carbide film that serves as an etching mask on the back surface of the silicon substrate , High frequency induction heating type CVD
Apparatus, the silicon substrate is arranged in the CVD device at a distance from the susceptor to be heated by induction, and the first silicon carbide film serving as a membrane and the second carbonization serving as an etching mask are provided on both surfaces of the silicon substrate. This is achieved by the method of manufacturing an X-ray mask according to the present invention, which includes a step of simultaneously depositing a silicon film.

[0010]

In other words, the high frequency induction heating type CVD according to the present invention
In the apparatus, the substrate to be grown (1) is placed apart (3) from the susceptor (2) within a range in which heating by the susceptor (2) is possible.

By doing so, the substrate to be grown is grown.
Sufficient growth gas is sent to the back surface (1B) side of (1), and it becomes possible to grow the deposited film on the front surface (1A) and back surface (1B) of the substrate to be grown (1) at the same time. Backside of growth substrate (1)
As with the surface (1A) side, it becomes possible to deposit a good-quality growth film (4) on the (1B) side, which has good adhesion.

Therefore, in the method of manufacturing the X-ray mask,
By using the CVD device according to the present invention to simultaneously form the SiC film for the membrane on the surface of the silicon substrate and the SiC film for the etching mask on the back surface, the vapor phase growth process of the SiC film on both sides of the silicon substrate. At the same time, the adhesion and the quality of the SiC film formed on both sides are improved, and the manufacturing yield can be improved.

[0013]

EXAMPLES The present invention will be described in detail below with reference to illustrated examples. FIG. 2 shows a high frequency induction heating type CV according to the present invention.
FIG. 3 is a schematic view of an embodiment of the D device, (a) is an axial sectional view,
(b) is a side sectional view taken along the line AA, (c) is a detailed view of the susceptor and the substrate supporting portion, FIG. 3 is a schematic view of another embodiment of the substrate supporting structure, (a) is a plan view, b) is a sectional view taken along the line A-A in FIG.
(a)-(f) is process sectional drawing of one Example of the manufacturing method of the X-ray mask which concerns on this invention. The same object is denoted by the same reference numeral throughout the drawings.

In FIG. 2, 11 is a silicon (Si) growth substrate, 11A is the front surface of the substrate, 11B is the back surface thereof, 12 is a carbon susceptor, 13 is a gap (separation part), and 14 is silicon carbide (Si).
C) Growth film, 15 quartz jig, 16 substrate and susceptor support, 17 quartz reaction tube, 18 growth gas inlet, 19 vacuum exhaust port, 20 quartz lid plate, 21 high frequency coil, 22A , 22B are protrusions for supporting the susceptor, and 23 is a groove for supporting the substrate.

High frequency induction heating type CVD according to the present invention
For example, as shown in FIGS. 2 (a) and 2 (b), the apparatus has a tubular shape having a growth gas inlet 18 and a vacuum exhaust port 19 on the side wall and one end of which is open, and the opening end is formed by a quartz cover plate 20. In the sealed quartz reaction tube 17, for example, by a semi-cylindrical quartz jig 15 as shown in the figure, the carbon susceptor 12 has reaction tubes at predetermined intervals via the susceptor and the substrate supporting portion 16 surrounded by the dotted line.
17 are vertically arranged in a direction directly facing the axial direction of 17 and, for example, on both sides of the carbon susceptor 12 via the substrate supporting portion 16.
A structure in which a Si substrate 11 is supported in parallel with the susceptor 12 with a predetermined gap 13 of about 0.5 to 5 mm, and a high frequency coil 21 used for induction heating of the susceptor 12 is arranged on the outer periphery of the quartz reaction tube 17. Have.

The susceptor and the substrate support portion 16 formed on the quartz jig 15 are supported by a pair of susceptors supported along the circumferential direction on the inner surface of the semi-cylindrical quartz jig 14 as shown in FIG. 3 (c). Projections 22A, 22B are formed at intervals so that the susceptor 12 can be gently inserted. The susceptor supporting projections 22A, 22B are formed.
It has a structure in which a substrate support groove 23 having a width into which the growth substrate 11 is gently fitted is formed at a position on the upper surface of B at a distance from the end surface on the susceptor side corresponding to the predetermined gap. In this jig, the susceptor 12 is inserted between the susceptor supporting protrusions 22A and 22B from above the jig, and the growth substrate 11 is inserted into the substrate support groove 23 from above the jig and supported. It

Then, a growth gas is introduced at a predetermined flow rate from the growth gas introduction port 18, and a predetermined evacuation is performed from the vacuum exhaust port 19 to keep the inside of the reaction tube 17 at a predetermined gas pressure by a high frequency coil. The carbon susceptor 12 is heated to a predetermined temperature by induction heating, and the Si growth substrate 11 is heated to a predetermined temperature by radiation and conduction heat from the susceptor 12, and a film of the reaction product on both surfaces of the growth substrate 11 is formed. Can grow.

With the apparatus for a 4-inch substrate having the structure of this embodiment, the reaction gas was changed to trichlorosilane (SiHC
l ₃ ): 50cc / min and propane (C ₃ H ₈ ): 300cc / min and hydrogen
(H ₂ ): Using a mixed gas of 7000 cc / min, adjust the gas pressure in the reaction tube 17 to about 3 to 3.5 Torr, and heat the susceptor 12 to about 1000 to 1150 ° C. by induction heating with 13.56 MHz high frequency. Then, the Si growth substrate 11 was heated to about 950 to 1050 ° C. by radiation and conduction heating from the susceptor 12 to perform vapor phase growth of the SiC film on both sides of the Si growth substrate 11.

Then, when the gap between the susceptor 12 and the Si substrate 11 is set to 2 mm and the growth of 2 μm is performed on the surface of the substrate 11,
We were able to form a good-quality SiC film with good adhesion on the back surface, with a film thickness almost the same as the front surface. In addition, the gap
When the thickness was 0.5 mm and 2.5 μm was grown on the front surface, a good quality SiC film with a thickness of 0.5 μm and good adhesion could be grown on the back surface. From the above, in the CVD apparatus according to the present invention, the growth film thickness ratio between the front and back can be adjusted to some extent by adjusting the gap between the susceptor and the growth substrate.

FIG. 3 shows another embodiment of the jig structure for positioning the growth substrate at a position near the susceptor at a predetermined distance from the susceptor. In this structure, the disk-shaped carbon susceptor 12 is provided with the board supporting protrusions 25 having the board guide grooves 24 having a width that allows the board to be gently inserted into the left and right sides, and the board can be gently inserted into the lower part. Substrate supporting protrusions 27 having shallow substrate supporting grooves 26 having various widths are provided.

Next, a method for manufacturing an X-ray mask according to the present invention, which uses the CVD apparatus according to the present invention, will be specifically described with reference to FIG. See FIG. 4 (a). For example, when forming an X-ray mask using a SiC film as a membrane material, for example, the C according to the present invention provided with the quartz jig having a distance of 1 mm between the susceptor and the substrate to be grown.
Si substrate having a diameter of, for example, 4 inches using a VD device
31 is set on a jig in the CVD apparatus, and the reaction gas is trichlorosilane (SiHCl ₃ ): 50 cc / min and propane (C
₃ H ₈ ): 300 cc / min and hydrogen (H ₂ ): 7,000 cc / min, the gas pressure inside the reaction tube 17 was adjusted to about 3 to 3.5 Torr, and induction heating was performed with a high frequency of 13.56 MHz. 12
Is heated to about 1000 to 1150 ° C., and the Si growth substrate 31 is heated to about 950 to 1050 ° C. by radiation and conduction heating from the susceptor 12, and the SiC for the membrane is formed on the surface of the Si substrate 31.
At the same time as growing the film 32A, an SiC film 32B for etching mask is grown on the back surface. The growth time is controlled so that the film thickness of the SiC film 32A for the membrane on the front surface is 2.5 μm, and 0.5 to 1 μm for the SiC film 32B for the etching mask on the back surface.
It is formed to a film thickness of about m. In the above growth, Si
Since the growth gas is sufficiently supplied to the back surface side of the substrate 31, the etching mask SiC film 32B formed on the back surface side of the Si substrate 31 is the SiC film for the membrane formed on the front surface side.
Similar to the film 32A, it is a high-quality film that is dense and has good adhesion.

See FIG. 4 (b). Then, the Si for membrane is sputtered as usual.
An X-ray absorber film 33 made of Ta is formed on the C film 32A. At this time, the surface of the SiC film 32A for membrane is dense and of good quality.
Since the SiC surface is exposed, the X-ray absorber film 33 has strong adhesion.

Next, referring to FIG. 4 (c), the Si substrate 31 is turned over, and the SiC for etching mask is used.
A resist film 34 is applied on the film 32B, exposed and developed to form a first etching window 35 corresponding to the first light-transmitting window to be formed on the Si substrate 31 on the resist film 34. Using the resist film 34 as a mask, dry etching is performed with CF ₄ gas or the like to form a second etching window 36 corresponding to the first light transmitting window in the etching mask SiC film 32B.

Next, after removing the resist film 34, the second light transmitting window 37 is formed on the Si substrate 31 with the etching mask SiC film 32B facing down.
It is adhered by an adhesive 39 on the ceramic support frame 38 having.

Next, as shown in FIG. 4 (e), the fluorine is sprayed through the second transparent window 38 of the ceramic support frame 38 and through the second etching window 36 with the etching mask SiC film 32B as a mask. The first transparent window 41 which exposes the back surface of the SiC film 32A for a membrane on the Si substrate 31 by performing back etching 40 on the Si substrate 31 with a nitric acid solution.
To form. At this point, a mask blank is completed in which the Si support frame 31F having the SiC film for membrane 32A and the X-ray absorber film 33 stretched on the upper surface is fixed on the ceramic support frame 38.

Next, referring to FIG. 4 (f), the X-ray absorber film 33 is selectively etched by the usual electron beam lithography technique to form the SiC film 32A.
An X-ray absorber pattern (mask pattern) 33P is formed on the SiC membrane 32M to complete the X-ray mask.

[0027]

As described in the above embodiments, in the high frequency induction heating type CVD apparatus according to the present invention, it is possible to simultaneously form a dense vapor phase growth film having good adhesiveness on both surfaces of the substrate to be grown. You can Therefore, by applying this CVD apparatus to the manufacture of an X-ray mask that requires the formation of a uniform coating on both sides, the manufacturing process is simplified and at the same time the accuracy of forming the Si support frame is improved and the absorber is The effect of preventing the peeling of the pattern is exerted and the yield can be improved.

Therefore, the present invention greatly contributes to simplifying the manufacturing process of the X-ray mask and improving the manufacturing yield.

[Brief description of drawings]

FIG. 1 is an explanatory view of the principle of the present invention.

FIG. 2 is a schematic diagram of a high frequency induction heating type CVD apparatus according to the present invention.

FIG. 3 is a schematic view of another embodiment of the substrate support structure according to the present invention.

FIG. 4 is a process cross-sectional view of an embodiment of a method for manufacturing an X-ray mask according to the present invention.

FIG. 5 is a process sectional view of a conventional X-ray mask manufacturing method.

FIG. 6 is a schematic cross-sectional view of a main part of a conventional high-frequency induction heating type CVD apparatus.

[Explanation of symbols]

 1 Growth Substrate 1A Growth Substrate Front Surface 1B Growth Substrate Backside 2 Susceptor 3 Separation Area 4 Chemical Vapor Deposition Film 11 Si Growth Substrate 11A is Si Growth Substrate Surface 11B is Si Growth Substrate Backside 12 Carbon Susceptor 13 Gap (distance) 14 SiC growth film 15 Quartz jig 16 Substrate and susceptor support 17 Quartz reaction tube 18 Growth gas inlet 19 Vacuum exhaust port 20 Quartz lid plate 21 High frequency coil 22A, 22B Susceptor supporting protrusion 23 Substrate support groove

Claims (2)

[Claims] 1. A high-frequency induction heating type chemical vapor deposition apparatus, which is arranged in a position near the susceptor separated from a susceptor for inductively heating a substrate to be grown and is substantially parallel to the susceptor. A chemical vapor deposition apparatus characterized in that a chemical vapor deposition film is simultaneously deposited on both sides. 2. When forming a first silicon carbide film that becomes a membrane on the surface of a silicon substrate that becomes a support frame and forming a second silicon carbide film that becomes an etching mask on the back surface of the silicon substrate, a high frequency wave is used. A first silicon carbide film that uses an induction heating type chemical vapor deposition apparatus and is arranged in the chemical vapor deposition apparatus apart from a susceptor for inductively heating the silicon substrate, and serves as a membrane on both surfaces of the silicon substrate. And a step of simultaneously depositing a second silicon carbide film to be an etching mask, the method of manufacturing an X-ray mask.